Care and/or make-up cosmetic composition structured with silicone polymers and organogelling agents, in rigid form

ABSTRACT

The invention relates to a care and/or make-up cosmetic composition comprising a liquid fatty phase comprising at least one silicone oil, structured with a gelling system comprising 
     1) at least one polymer having a weight-average molecular mass ranging from 500 to 500 000, containing at least one moiety comprising: 
     
         
         
           
             at least one polyorganosiloxane group consisting of 1 to 1 000 organosiloxane units in the chain of the moiety or in the form of a graft, and 
             at least two groups capable of establishing hydrogen interactions,
 
the polymer being solid at room temperature and soluble in the liquid fatty phase at a temperature of 25 to 250° C., and
 
2) at least one non-polymeric organogelling agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Phase Application based onPCT/EP03/06463, filed on Jun. 2, 2003, which claims the priority ofFrench Application No. 0207206, filed on Jun. 12, 2002, and the benefitof U.S. Provisional Application No. 60/391,617, filed on Jun. 27, 2002,the contents of all of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a care and/or treatment and/or make-upcosmetic composition for the skin, including the scalp, and/or the lipsof human beings, containing a liquid fatty phase comprising at least onesilicone oil, gelled with a particular polymer, provided in particularin the form of a cast make-up product, in particular as a make-up sticksuch as lipsticks, whose application leads to a glossy and non-migratingdeposit.

A care and/or treatment cosmetic composition is a composition whichcomprises at least one active compound for treating wrinkles, formoisturizing the skin and the lips, for protecting the skin, the lipsand superficial body growths from ultraviolet rays, for treating acneand/or for acting as self-tanning agent.

The invention relates more particularly to cosmetic and dermatologicalcompositions such as make-up products exhibiting properties of stayingpower, non-transfer and stability.

PRIOR STATE OF THE ART

In cosmetic or dermatological products, it is common to find astructured, namely gelled and/or rigidified, liquid fatty phase; this isin particular the case in solid compositions such as deodorants, balmsand lipsticks, eyeshadows, concealer products and foundations which havebeen cast. This structuring is obtained with the aid of waxes orfillers. Unfortunately, these waxes and fillers tend to mattify thecomposition, which is not always desirable in particular for a lipstickor an eyeshadow.

The expression liquid fatty phase is understood to mean, for thepurposes of the application, a fatty phase which is liquid at roomtemperature (25° C.) and atmospheric pressure (760 mmHg), which iscomposed of one or more fatty substances which are liquid at roomtemperature, which are also called oils, which are compatible with eachother and which contain a silicone oil.

The expression structured liquid fatty phase is understood to mean, forthe purposes of the application, that this structured phase does not rununder its own weight.

The structuring of the liquid fatty phase makes it possible inparticular to limit its exudation from solid compositions and,furthermore, to limit, after deposition on the skin or the lips, themigration of this phase into wrinkles and fine lines, which isparticularly sought for a lipstick or an eyeshadow. Indeed, substantialmigration of the liquid fatty phase, charged with colouring matter,leads to an inaesthetic effect around the lips or the eyes, particularlyaccentuating the wrinkles and fine lines. This migration is often citedby women as a major defect of conventional lipsticks or eyeshadows. Theexpression migration is understood to mean an overflowing of thecomposition deposited on the skin or the lips, outside its initialoutline.

The gloss is mainly linked to the nature of the liquid fatty phase.Thus, it is possible to reduce the amount of waxes and fillers in thecomposition in order to increase the gloss of a lipstick, but then themigration of the liquid fatty phase increases. In other words, theamounts of waxes and fillers necessary for producing a stick of suitablehardness are a barrier to the gloss of the deposit.

The document EP-A-1 068 856 [1] describes solid cosmetic compositions,with no wax, containing a liquid fatty phase structured with a polymer,in which the fatty phase is mainly a non-silicone oil.

The document WO-A-01/97758 [2] describes cosmetic compositions based onpolyamide resins comprising a gelling agent chosen from esters andamides of N-acylamino acids and mixtures thereof. The composition alsocomprises a solvent for the polyamide resin which may be chosen fromunsaturated and saturated fatty alcohols, fatty and/or aromaticcarboxylic acid esters, ethoxylated and/or propoxylated alcohols andacids, silicones, mineral oils and branched-chain hydrocarbons;preferably, fatty acid esters, fatty alcohols, mineral oils, branchedhydrocarbons and mixtures thereof.

The use of fatty phases based on silicone oils makes it possiblecurrently to obtain cosmetic compositions having a long staying powerwhen the oils are only slightly volatile or are non-volatile, namely agood staying power in particular of the colour over time (unchanging,unfading), and transfer-free compositions when the silicone oils arevolatile, not forming a deposit on a support such as a glass, a cup, afabric or a cigarette, placed in contact with the film of make-up.

Currently, the use of silicone oils in cosmetics is limited by the smallnumber of molecules which can gel these media and thus give compositionswhich exist in solid form such as lipsticks or cast foundations forexample. The use of cosmetic compositions whose fatty phase ispredominantly siliconized leads, in most cases, to problems ofcompatibility with the ingredients conventionally used in cosmetics.

In the documents U.S. Pat. No. 5,874,069 [3], U.S. Pat. No. 5,919,441[4], U.S. Pat. No. 6,051,216 [5], WO-A-99/06473 [40], U.S. Pat. No.6,353,076 [41], WO-A-02/17870 [6], and WO-A-02/17871 [7], cosmeticcompositions such as deodorant sticks or gels, comprising a siliconeoily phase gelled with a polysiloxane- and polyamide-based wax, or witha polymer containing siloxane groups and groups capable of hydrogeninteractions, have been prepared.

In WO-A-02/17870 [6], it is envisaged to add to the composition anothergelling agent, but the quantities added should be low, for example lessthan 0.5% in the case of hydroxystearic acid, in order to preserve theclarity of the product.

In WO-A-02/17871 [7], it is also envisaged to use a second gelling agentwith the silicone polymer in a quantity representing 0.5 to 2% by weightof the composition, and a solvent system comprising a non-siliconeorganic compound, a volatile silicone and optionally another silicone.

The document EP-A-1 177 784 [8] illustrates a deodorant compositioncomprising a liquid phase containing, for example, a volatile siliconeand optionally a non-volatile silicone and/or a non-silicone hydrophobicorganic liquid, structured with an organic compound with amido groups,with optionally one or more polymeric or non-polymeric secondarystructuring agents in small proportions. Among the secondary structuringagents, this document mentions polymers having siloxane groups andgroups exhibiting hydrogen interactions without giving examples orresults on a composition using these polymers.

It should be stated that the documents [6], [7] and [8] relate todeodorants for which the problems of exudation and migration of theliquid fatty phase charged with colouring matter into wrinkles and finelines, and of staying power and non-transfer of the composition, do notexist as in the case of the make-up cosmetic products described above.Moreover, no gloss is sought for deodorants.

In addition, the sticks obtained by structuring the liquid fatty phasewith solely one or more gelling silicone polymers do not exhibitsufficient mechanical resistance to shearing, in particular during theapplication of the stick to the lips and/or the skin, leading tobreaking of the stick.

DISCLOSURE OF THE INVENTION

The subject of the invention is precisely a care and/or make-up and/ortreatment composition for the skin and/or the lips, which makes itpossible to overcome the disadvantages mentioned above.

Surprisingly, the applicant has found that the use of particularpolymers combined with one or more non-polymeric organogelling agentsmade it possible to structure, in the absence or in the presence ofsmall quantities of wax, the silicone oil-based liquid fatty phases, inthe form of a make-up or care product whose application led to a glossy,satiny or matt film according to the wishes of the user and/or the typeof non-migrating product desired, and to reinforce the staying powerand/or transfer-free properties of these products. In addition, theirheat-stability is enhanced.

The expression stable is understood to mean a composition which does notexude at room temperature (25° C.) for at least 2 months, or even up to9 months.

The combination of these polymers with one or more organogelling agentsmakes it possible to obtain gels, in particular solid gels, having agood mechanical strength and an acceptable rheology in order to allow adeposit in a sufficient quantity which does not feel sticky, which has avery good staying power, which is transfer-free (in particular whenvolatile silicone oils are used) and which does not migrate intowrinkles and fine lines.

The effects obtained by virtue of this combination do not appear in thedocuments relating to deodorants which possibly envisage thiscombination since the problems solved by this combination do not existin the field of deodorants.

The invention not only applies to make-up products for the lips such aslipsticks, lip pencils and lip glosses, but also to care and/ortreatment products for the skin, including the scalp, and the lips, suchas sun protection products in stick form for the skin, the face or thelips, or lip balms, to make-up products for the skin, both of the faceand of the human body, such as foundations cast as a stick or in a dish,concealer products and temporary tattoo products, to cleansing products,in particular in stick form, and to make-up products for the eyes suchas eyeliners, in particular in pencil form, and mascaras, in particularcakes for keratinous fibres (eyelashes, eyebrows, hair).

More precisely, the subject of the invention is a care and/or make-upcosmetic composition comprising a liquid fatty phase comprising at leastone silicone oil, structured with at least one gelling system comprising

a) at least one polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions, chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one of the groups is different from an ester group, and        b) at least one non-polymeric organogelling agent, the liquid        fatty phase and the gelling system forming a physiologically        acceptable medium.

According to the invention, the expression “gelling system” isunderstood to mean a system which makes it possible to rigidify thecomposition by forming hydrogen bonds.

The composition of the invention may be provided in the form of a paste,a solid or a more or less viscous cream. It may be a simple or multiple,in particular an oil-in-water or a water-in-oil, emulsion, a rigid orsoft gel having an oily continuous phase. The simple or multipleemulsion may comprise an aqueous or oily continuous phase optionallycontaining dispersed lipid vesicles. In particular, it is provided in aform cast as a stick or in a dish and more especially in the form of anoily, in particular anhydrous, rigid gel and in particular of ananhydrous stick. More especially, it is provided in the form of atranslucent or opaque rigid gel (according to whether it containspigments or otherwise), the liquid fatty phase forming the continuousphase. An anhydrous composition will comprise less than 10% by weight ofwater, for example less than 5% by weight.

The structuring of the liquid fatty phase can be modulated according tothe nature of the polymer and the non-polymeric organogelling agent usedin the gelling system, and may be such that a rigid structure isobtained in the form of a baton or a stick, having good mechanicalstrength. When they are coloured, these batons make it possible, afterapplication, to obtain a glossy deposit, which does not migrate andwhich has good staying power, in particular of the colour over time. Thecomposition may comprise one or more structuring polymers and one ormore non-polymeric organogelling agents.

Advantageously, the composition of the invention is a composition forthe lips and even better a lipstick composition in particular in stickform.

Liquid Fatty Phase

According to the invention, the liquid fatty phase comprises at leastone silicone oil which may be a volatile oil, a non-volatile oil or amixture of volatile oil(s) and of non-volatile oil(s). An oil is anon-aqueous compound which is immiscible with water.

According to the invention, the volatile silicone oil may be chosen fromlinear or cyclic silicone oils having a flash point equal to or greaterthan 40° C. and advantageously greater than the softening point of thegelling system and/or a viscosity of less than 8 cSt, such as linear orcyclic polydimethylsiloxanes (PDMS) having from 3 to 7 silicon atoms.

By way of examples of such volatile oils, there may be mentioned thecompounds given in Table 1 below.

The non-volatile silicone oils may be polydimethylsiloxanes,polyalkylmethylsiloxanes, dimethicone copolyols, alkylmethiconecopolyols, cetyldimethicone, silicones with alkylglyceryl ether groups,silicones with side amine groups and dilauroyltrimethylol propanesiloxysilicate. The alkyl groups of these oils have in particular from 2to 24 carbon atoms.

The non-volatile silicone oils which can be used in the invention may bein particular linear, non-volatile polydimethylsiloxanes (PDMS) whichare liquid at room temperature; polydimethylsiloxanes containing alkyl,alkoxy or phenyl groups, which are pendent and/or at the silicone chainend, groups each having from 2 to 24 carbon atoms; phenylated siliconessuch as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones,diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, fluorinated silicones with one or moregroup(s) that is (are) pendent or at the chain end having from 1 to 12carbon atoms of which all or some of the hydrogen atoms are substitutedwith fluorine atoms, dimethiconols and mixtures thereof.

According to the invention, the liquid fatty phase may comprise at leastone volatile silicone oil and at least one volatile non-silicone oil.

For the purposes of the invention, a volatile silicone or non-siliconeoil has a flash point preferably of 40 to 135° C. or no flash point.Volatile oils have at room temperature (25° C.) and atmospheric pressure(760 mmHg) a vapour pressure ranging from 0.02 mm to 300 mmHg (2.66 Pato 40 000 Pa) and even better ranging from 0.1 to 90 mmHg (13 Pa to 12000 Pa). The non-volatile oils then correspond to a vapour pressure ofless than 0.02 mmHg (2.66 Pa).

The silicone oils of the invention have a viscosity which isadvantageously chosen from the ranging going from 5 to 800 000 cSt at25° C., preferably from 10 to 500 000 cSt, and even better from 10 to 5000 cSt.

TABLE 1 Flash point Viscosity Compound (° C.) (cSt) Octyltrimethicone 931.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2(cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane 55 2.5(cyclotetradimethylsiloxane or D4) Dodecamethylcyclohexasiloxane (D6) 937 Decamethyltetrasiloxane (L4) 63 1.7 KF 96 A from Shin Etsu 94 6 PDMS(polydimethylsiloxane) DC 200 56 1.5 (1.5 cSt) from Dow Corning PDMS DC200 (2 cSt) from Dow 87 2 Corning PDMS DC 200 (5 cSt) 134 5 cSt from DowCorning PDMS DC 200 (3 cSt) 102 3 cSt from Dow Corning

The volatile silicone oil may also be chosen from the group comprisingfluorinated silicone oils such as silicones with alkyl andperfluoroalkyl groups, silicones with oxyethylenated/oxypropylenated(EO/PP) side groups and with perfluorinated groups, silicones withperfluorinated side groups and with glycerolated side groups,perfluoroalkylmethylphenyl-siloxanes, these oils having a vapourpressure greater than or equal to 0.02 mmHg.

According to the invention, the liquid fatty phase may contain one ormore volatile or non-volatile non-silicone oils. The volatilenon-silicone oils may be chosen from the group comprising hydrocarbonoils and volatile esters and ethers such as volatile hydrocarbons suchas isododecane and isohexadecane, C₈-C₁₆ isoparaffins, isohexyl orisodecyl neopentanoates.

The volatile non-silicone oil may also be chosen from fluorinated oilssuch as perfluoropolyethers, perfluoroalkanes such as perfluorodecalin,perfluorodamantanes, monoesters, diesters and triesters ofperfluoroalkyl phosphates and fluorinated ester oils.

By way of example of volatile non-silicone oils which can be used in theinvention, there may be mentioned the compounds of Table 2 whichfollows.

TABLE 2 Flash point Compound (° C.) Isododecane 43 Isohexadecane 102Isodecyl neopentanoate 118 Propylene glycol n-butyl ether 60 Ethyl3-ethoxypropionate 58 Propylene glycol methyl ether 46 acetate* Isopar L(C₁₁-C₁₃ isoparaffin) 62 Isopar H (C₁₁-C₁₂ isoparaffin) 56

The liquid fatty phase advantageously contains at least 30%, and evenbetter at least 40% by weight of silicone oil(s) advantageously having aviscosity of less than 1 000 cSt and even better of less than 100 cStbecause the silicone polymers used in the invention are more soluble insilicone oils of low viscosity. It may also contain other non-siliconeoils or a mixture of non-silicone oils.

When the fatty phase comprises a volatile oil, it advantageouslyrepresents from 3 to 89.4%, and even better from 5 to 60%, for examplefrom 5 to 10% of the total weight of the composition.

The liquid fatty phase may also contain other non-silicone oils, forexample polar oils such as:

hydrocarbonaceous vegetable oils with a high content of triglyceridesconsisting of esters of fatty acids and of glycerol in which the fattyacids may have varied chain lengths, it being possible for the latter tobe linear or branched, saturated or unsaturated; these oils are inparticular wheat germ, maize, sunflower, karite, castor, sweet almond,macadamia, apricot, soybean, rapeseed, cottonseed, lucerne, poppy seed,pumpkin seed, sesame, gourd, avocado, hazelnut, grapeseed orblackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye,safflower, candlenut, passion flower and rose musk oils; ortriglycerides of caprylic/capric acids such as those sold by the companyStearines Dubois or those sold under the names Miglyol 810, 812 and 818by the company Dynamit Nobel;

synthetic oils or esters of formula R₅COOR₆ in which R₅ represents theresidue of a linear or branched higher fatty acid containing from 1 to40 and even better from 7 to 19 carbon atoms and R₆ represents abranched hydrocarbon chain containing from 1 to 40 and even better from3 to 20 carbon atoms, with R₅+R₆≧10 such as, for example, Purcellin oil(ketostearyl octanoate), isononyl isononanoate, C₁₂ to C₁₅ alcoholbenzoate, isopropyl myristate, 2-ethylhexyl palmitate, octanoates,decanoates or ricinoleates of alcohols or of polyalcohols; hydroxylatedesters such as isostearyl lactate, diisostearyl malate; and esters ofpentaerythritol;

synthetic esters having from 10 to 40 carbon atoms;

C₈ to C₂₆ fatty alcohols such as oleyl alcohol and octyldodecanol;

fatty acids such as oleic, linoleic or linolenic acid; and

mixtures thereof.

The liquid fatty phase may also contain apolar oils such as linear orbranched hydrocarbons or fluorocarbons of synthetic or mineral origin,which are volatile or not, such as volatile oils of paraffin (such asisoparaffins, isododecane) or non-volatile oils of paraffin and itsderivatives, petroleum jelly, polydecenes, hydrogenated polyisobutenesuch as parleam, squalane, and mixtures thereof.

Generally, the liquid fatty phase represents from 5 to 99% of the totalweight of the composition and even better from 20 to 75%.

Solid Particles

According to the invention, the composition generally comprises, inaddition, solid particles chosen from fillers and pigments. Generally,the mean size of the solid particles is from 10 nm to 50 μm, and evenbetter from 50 nm to 30 μm, for example from 100 nm to 10 μm.

The fillers used in the cosmetic compositions are generally intended toabsorb sweat and sebum and/or to provide mattness. According to theinvention, they further make it possible to structure the liquid fattyphase containing a silicone oil and to reinforce the staying powerand/or transfer-free properties of the composition and also the heatstability.

The expression pigments is understood to mean any solid particleinsoluble in the composition which serves to give and/or modify a colourand/or an iridescent appearance.

These pigments may simultaneously provide the function of absorption ofsweat and of sebum, and the function of coloration or of modification ofappearance of the composition, that is of the make-up and/or carecosmetic product. In the invention, they also bring about thestructuring of the liquid fatty phase.

These fillers or pigments may be either of a hydrophobic nature, or of ahydrophilic nature. When these fillers or pigments are hydrophilicparticles, their dispersion in the composition is facilitated either bycoating them with a film of hydrophobic compound or by adding adispersant and in particular an amphiphilic silicone to the composition.

The hydrophobic pigments or fillers may consist of hydrophobic polymeror copolymer powders. By way of example of hydrophobic polymers andcopolymers used as fillers, there may be mentioned:

1) fluorinated polymers such as polytetrafluoroethylene powders andtetrafluoroethylene and olefin, for example ethylene or propylene,copolymer powders; 2) silicone elastomers, for examplepolymethylsilsesquioxane powders (Tospearl® from Toshiba); 3)polyolefins such as polyethylene; 4) polyalkyl methacrylates, forexample polymethyl methacrylate; 5) polyamides (Nylon®); 6)polystyrenes; 7) polyesters and derivatives thereof; 8) polyacrylics(Polytrap® from Dow Corning) or polymethyl methacrylate; and 9)polyurethanes, for example hexamethylene diisocyanate/trimethylolhexalactone powders.

It is also possible to use hydrophilic fillers which are surface-treatedso as to be hydrophobic, such as boron nitride, starch, precipitatedcalcium carbonate, silica, glass, or a ceramic.

Instead of powders, it is of course possible to use fibres of ahydrophobic nature, in particular fibres of the polymers and copolymersmentioned above.

The solid particles may also consist of pigments and/or pearlescentagents which make it possible to obtain a make-up with high coverage,that is to say which does not reveal the skin, the lips or thesuperficial body growths. These particles make it possible, in addition,to reduce the sticky feel of the compositions.

The pigments may be white or coloured, inorganic and/or organic, coatedor not. There may be mentioned, among the inorganic pigments, titaniumor zinc dioxide, optionally surface-treated, zirconium or cerium oxides,and iron or chromium oxides, manganese violet, ultramarine blue,chromium hydrate and ferric blue. Among the organic pigments, there maybe mentioned carbon black, pigments of the D & C type, and lacquersbased on carmine, barium, strontium, calcium or aluminium. The pigmentsmay represent from 0.1 to 50%, preferably from 0.5 to 40%, and evenbetter from 2 to 30% of the total weight of the composition.

The pearlescent pigments (or pearlescent agents) may be chosen fromwhite pearlescent pigments such as mica coated with titanium, or withbismuth oxychloride, coloured pearlescent pigments such as mica-titaniumwith iron oxides, mica-titanium with in particular ferric blue andchromium oxide, mica-titanium with an organic pigment of theabovementioned type and pearlescent pigments based on bismuthoxychloride. The pearlescent pigments may also have goniochromaticproperties and may be provided in the form of liquid crystals ormultilayer platelets. They may represent from 0 to 30% of the totalweight of the composition, and even better from 0.1 to 20%.

When the pigments or fillers are hydrophilic, they are coated with afilm of hydrophobic compound so as to introduce them into the liquidfatty phase of the composition of the invention.

The coating may be a fluorinated coating such as a perfluoroalkyl mono-or diester of phosphoric acid, (acid or salt), a perfluoropolyether, aperfluorocarboxylic or -sulfonic acid, or a perfluoroalkyl phosphatesalt of diethanolamine.

The coating may be a coating based on a fluorinated silicone, forexample a coating-grafting with a silane having a perfluoroalkyl group.

The coating may also be carried out by means of silicone derivatives,for example a coating-grafting with reactive silicones initiallypossessing hydrogenosilane groups, a coating-grafting with adiorganosilane such as dimethylchlorosilane or with analkylalkoxysilane, a coating-grafting with a silane having aglycydoxypropyl group, a coating with a polyglycerolated silicone, or acoating with a silicone-g-polyacrylic or silicone grafted acryliccopolymer.

It is also possible to use a coating with N-acylamino acids, for exampleN-lauroyllysine, coatings with fatty acids or fatty acid salts of thestearic acid type, coatings with lecithins and coatings with ester oils.

It is also possible to facilitate the dispersion of the hydrophilicparticles by means of at least one amphiphilic silicone which plays therole of a surfactant between the hydrophilic particles and thehydrophobic silicone phase.

These amphiphilic silicones contain a silicone part which is compatiblewith the highly siliconized medium of the compositions of the invention,and a hydrophilic part which may be, for example, the residue of acompound chosen from alcohols and polyols, having from 1 to 12 hydroxylgroups, polyoxyalkylenes containing at least two oxyalkylenated moietiesand having from 0 to 20 oxypropylenated moieties and/or from 0 to 20oxyethylenated moieties. This hydrophilic part therefore has affinityfor the hydrophilic particles and promotes their dispersion in thesilicone medium.

The amphiphilic silicone may be an oil with no gelling activity. Suchoils may consist of:

dimethicone copolyols, optionally containing phenyl groups,

alkylmethicone copolyols,

polyglycerolated silicones, that is to say silicones with alkylglycerylether groups,

silicones with perfluorinated side groups and with glycerolated sidegroups,

silicones with polyoxyethylenated/polyoxypropylenated side groups andwith perfluorinated side groups,

copolymers with a silicone block and with a hydrophilic block other thanpolyether, for example polyoxazoline or polyethyleneimine,

graft copolymers of the silicone-grafted polysaccharide type,

copolymers with a silicone block and with apolyoxyethylene/polyoxypropylene block.

The amphiphilic silicone used in the invention may also be anamphiphilic silicone resin which is at least partially crosslinked.

By way of example of such resins, there may be mentioned:

crosslinked silicone resins with alkyl polyether groups, such aspolyoxyethylene (POE) and polyoxyethylene/polyoxypropylene (POE/POP),described in U.S. Pat. No. 5,412,004 [9], and

silicone resins partially crosslinked with α,ω-dienes, possessing bothhydrophilic POE/POP side chains and hydrophobic alkyl side chains suchas those described in EP-A-1 048 686 [10]. The hydrophilic side chainsare obtained by reaction with a POE/POP having only one vinyl end, andthe alkyl side chains are formed by reaction with an α-olefin having afatty chain.

In the amphiphilic silicone resin, the silicone part advantageouslyconsists of polydimethylsiloxane.

Gelling Silicone Polymer

The structuring or gelling polymer(s) of the composition are solid atroom temperature (25° C.) and atmospheric pressure (760 mmHg) and aresoluble in the liquid fatty phase at a temperature of 25 to 250° C.

The expression polymer is understood to mean, for the purpose of theinvention, a compound having at least 2 repeating moieties, preferablyat least 3 repeating moieties and even better 10 repeating moieties.

In the composition of the invention, the silicone polymer of the gellingsystem generally represents from 0.5 to 80%, preferably from 2 to 60%and even better from 5 to 40% of the total weight of the composition.

Moreover, the polymer of the gelling system/silicone oil(s) mass ratiois preferably from 0.1 to 50%.

The polymers used as gelling agents in the composition of the inventionare polymers of the polyorganosiloxane type such as those described inthe documents U.S. Pat. No. 5,874,069 [3], U.S. Pat. No. 5,919,441 [4],U.S. Pat. No. 6,051,216 [5] and U.S. Pat. No. 5,981,680 [11].

According to the invention, the polymers used as gelling agent maybelong to the following two families:

1) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being situated inthe polymer chain; and/or

2) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being situated onthe grafts or branches.

The polymers to which the invention applies are solids which may besolubilized beforehand in a solvent with hydrogen interactions, capableof breaking the hydrogen interactions of the polymers, such as C₂ to C₈lower alcohols and in particular ethanol, n-propanol or isopropanol,before being brought into contact with the silicone oils according tothe invention. It is also possible to use these hydrogen interaction“breaking” solvents as cosolvent. These solvents may then be kept in thecomposition or may be removed by selective evaporation which is wellknown to persons skilled in the art.

The polymers comprising two groups capable of establishing hydrogeninteractions in the polymer chain may be polymers comprising at leastone moiety corresponding to the formula:

in which:

-   -   1) R¹, R², R³ and R⁴ which may be identical or different,        represent a group chosen from:        -   linear, branched or cyclic, saturated or unsaturated, C₁ to            C₄₀ hydrocarbon-based groups, possibly containing in their            chain one or more oxygen, sulphur and/or nitrogen atoms, and            possibly being partially or totally substituted with            fluorine atoms,        -   C₆ to C₁₀ aryl groups, optionally substituted with one or m            ore C₁ to C₄ alkyl groups,        -   polyorganosiloxane chains possibly containing one or more            oxygen, sulphur and/or nitrogen atoms;    -   2) the groups X, which may b e identical or different, represent        a linear or branched C₁ to C₃₀ alkylenediyl group, possibly        containing in its chain one or more oxygen and/or nitrogen        atoms;    -   3) Y is a saturated or unsaturated, C₁ to C₅₀ linear or branched        divalent alkylene, arylene, cycloalkylene, alkylarylene or        arylalkylene group, possibly comprising one or more oxygen,        sulphur and/or nitrogen atoms, and/or bearing as substituent one        of the following atoms or groups of atoms: fluorine, hydroxyl,        C₃ to C₈ cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyl        optionally substituted with 1 to 3 C₁ to C₃ alkyl groups, C₁ to        C₃ hydroxyalkyl and C₁ to C₆ aminoalkyl, or    -   4) Y represents a group corresponding to the formula:

in which

-   -   T represents a linear or branched, saturated or unsaturated, C₃        to C₂₄ trivalent or tetravalent hydrocarbon-based group        optionally substituted with a polyorganosiloxane chain, and        possibly containing one or more atoms chosen from O, N and S, or        T represents a trivalent atom chosen from N, P and Al, and    -   R⁵ represents a linear or branched C₁ to C₅₀ alkyl group or a        polyorganosiloxane chain, possibly comprising one or more ester,        amide, urethane, thiocarbamate, urea, thiourea and/or        sulphonamide groups, which may possibly be linked to another        chain of the polymer;    -   5) the groups G, which may be identical or different, represent        divalent groups chosen from:

in which R⁶ represents a hydrogen atom or a linear or branched C₁ to C₂₀alkyl group, on condition that at least 50% of the groups R⁶ of thepolymer represent a hydrogen atom and that at least two of the groups Gof the polymer are a group other than:

-   -   6) n is an integer ranging from 2 to 500 and preferably from 2        to 200, and m is an integer ranging from 1 to 1 000, preferably        from 1 to 700 and better still from 6 to 200.

According to the invention, 80% of the groups R¹, R², R³ and R⁴ of thepolymer are preferably chosen from methyl, ethyl, phenyl and3,3,3-trifluoropropyl groups.

According to the invention, Y can represent various divalent groups,furthermore optionally comprising one or two free valencies to establishbonds with other moieties of the polymer or copolymer. Preferably, Yrepresents a group chosen from:

a) linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups,

b) C₃₀ to C₅₆ branched alkylene groups possibly comprising rings andunconjugated unsaturations,

c) C₅-C₆ cycloalkylene groups,

d) phenylene groups optionally substituted with one or more C₁ to C₄₀alkyl groups,

e) C₁ to C₂₀ alkylene groups comprising from 1 to 5 amide groups,

f) C₁ to C₂₀ alkylene groups comprising one or more substituents chosenfrom hydroxyl, C₃ to C₈ cycloalkane, C₁ to C₃ hydroxyalkyl and C₁ to C₆alkylamine groups,

g) polyorganosiloxane chains of formula:

in which R¹, R², R³, R⁴, T and m are as defined above, and

h) polyorganosiloxane chains of formula:

The polyorganosiloxanes of the second family may be polymers comprisingat least one moiety corresponding to formula (II):

in which

R¹ and R³, which may be identical or different, are as defined above forformula (I),

R⁷ represents a group as defined above for R¹ and R³, or represents thegroup of formula —X-G-R⁹ in which X and G are as defined above forformula (I) and R⁹ represents a hydrogen atom or a linear, branched orcyclic, saturated or unsaturated, C₁ to C₅₀ hydrocarbon-based groupoptionally comprising in its chain one or more atoms chosen from O, Sand N, optionally substituted with one or more fluorine atoms and/or oneor more hydroxyl groups, or a phenyl group optionally substituted withone or more C₁ to C₄ alkyl groups,

R⁸ represents the group of formula —X-G-R⁹ in which X, G and R⁹ are asdefined above,

m₁ is an integer ranging from 1 to 998, and

-   -   m₂ is an integer ranging from 2 to 500.

According to the invention, the polymer used as gelling agent may be ahomopolymer, that is to say a polymer comprising several identicalmoieties, in particular moieties of formula (I) or of formula (II).

According to the invention, it is also possible to use a polymerconsisting of a copolymer comprising several different moieties offormula (I), that is to say a polymer in which at least one of thegroups R¹, R², R³, R⁴, X, G, Y, m and n is different in one of themoieties. The copolymer may also be formed from several moieties offormula (II), in which at least one of the groups R¹, R³, R⁷, R⁸, m₁ andm₂ is different in at least one of the moieties.

It is also possible to use a copolymer comprising at least one moiety offormula (I) and at least one moiety of formula (II), the moieties offormula (I) and the moieties of formula (II) possibly being identical toor different from each other.

According to one variant of the invention, it is also possible to use acopolymer furthermore comprising at least one hydrocarbon-based moietycomprising two groups capable of establishing hydrogen interactions,chosen from ester, amide, sulphonamide, carbamate, thiocarbamate, urea,thiourea, oxamido, guanidino and biguanidino groups, and combinationsthereof. These copolymers may be block copolymers or graft copolymers.

According to a first embodiment of the invention, the groups capable ofestablishing hydrogen interactions are amide groups of formulae —C(O)NH—and —HN—C(O)—.

In this case, the gelling agent may be a polymer comprising at least onemoiety of formula (III) or (IV):

in which R¹, R², R³, R⁴, X, Y, m and n are as defined above.

Such a moiety may be obtained:

either by a condensation reaction between a silicone containingα,ω-carboxylic acid ends and one or more diamines, according to thefollowing reaction scheme:

or by reaction of two molecules of α-unsaturated carboxylic acid with adiamine according to the following reaction scheme:

followed by the addition of a siloxane to the ethylenic unsaturations,according to the following scheme:

in which X¹—(CH₂)₂— corresponds to X defined above and Y, R¹, R², R³, R⁴and m are as defined above;

or by reaction of a silicone containing α,ω-NH₂ ends and a diacid offormula HOOC—Y—COOH according to the following reaction scheme:

In these polyamides of formula (III) or (IV), m is preferably in therange from 1 to 700, more preferably from 15 to 500 and better stillfrom 15 to 45, and n is in particular in the range from 1 to 500,preferably from 1 to 100 and better still from 4 to 25,

X is preferably a linear or branched alkylene chain containing from 1 to30 carbon atoms and in particular 3 to 10 carbon atoms, and

Y is preferably an alkylene chain that is linear or branched or thatpossibly comprises rings and/or unsaturations, containing from 1 to 40carbon atoms, in particular from 1 to 20 carbon atoms and better stillfrom 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y canoptionally contain in its alkylene portion at least one of the followingelements:

1) 1 to 5 amide, urea or carbamate groups,

2) a C₅ or C₆ cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical ordifferent C₁ to C₃ alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substitutedwith at least one element chosen from the group consisting of:

a hydroxyl group,

a C₃ to C₈ cycloalkyl group,

one to three C₁ to C₄₀ alkyl groups,

a phenyl group optionally substituted with one to three C₁ to C₃ alkylgroups,

a C₁ to C₃ hydroxyalkyl group, and

a C₁ to C₆ aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

in which R⁵ represents a polyorganosiloxane chain and T represents agroup of formula:

in which a, b and c are, independently, integers ranging from 1 to 10,and R¹⁰ is a hydrogen atom or a group such as those defined for R¹, R²,R³ and R⁴.

In formulae (III) and (IV), R¹, R², R³ and R⁴ preferably represent,independently, a linear or branched C₁ to C₄₀ alkyl group, preferably aCH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or aphenyl group optionally substituted with one to three methyl or ethylgroups.

As has been seen previously, the polymer may comprise identical ordifferent moieties of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several moieties offormula (III) or (IV) of different lengths, i.e. a polyamidecorresponding to the formula:

in which X, Y, n and R¹ to R⁴ have the meanings given above, m₁ and m₂,which are different, are chosen in the range from 1 to 1 000, and p isan integer ranging from 2 to 300.

In this formula, the moieties may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer. In thiscopolymer, the moieties may be not only of different lengths, but alsoof different chemical structures, for example containing differentgroups Y. In this case, the copolymer may correspond to the formula:

in which R¹ to R⁴, X, Y, m₁, m₂, n and p have the meanings given aboveand Y¹ is different from Y but chosen from the groups defined for Y. Aspreviously, the various moieties may be structured to form either ablock copolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the gelling agent may alsoconsist of a graft copolymer. Thus, the polyamide containing siliconeunits may be grafted and optionally crosslinked with silicone chainscontaining amide groups. Such polymers may be synthesized withtrifunctional amines.

In this case, the copolymer may comprise at least one moiety of formula:

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹¹ to R¹⁸ are groups chosen from the samegroup as R¹ to R⁴, m₁ and m₂ are numbers in the range from 1 to 1000,and p is an integer ranging from 2 to 500.

In formula (VII), it is preferred that:

p is in the range from 1 to 25 and better still from 1 to 7,

R¹¹ to R¹⁸ are methyl groups,

T corresponds to one of the following formulae:

in which R¹⁹ is a hydrogen atom or a group chosen from the groupsdefined for R¹ to R⁴, and R²⁰, R²¹ and R²² are, independently, linear orbranched alkylene groups, and more preferably corresponds to theformula:

in particular with R²⁰, R²¹ and R²² representing —CH₂—CH₂—,

m₁ and m₂ are in the range from 15 to 500 and better still from 15 to45,

X¹ and X² represent —(CH₂)₁₀—, and

Y represents —CH₂—.

These polyamides containing a grafted silicone moiety of formula (VII)may be copolymerized with polyamide-silicones of formula (II) to formblock copolymers, alternating copolymers or random copolymers. Theweight percentage of grafted silicone moieties (VII) in the copolymermay range from 0.5% to 30% by weight.

According to the invention, as has been seen previously, the siloxaneunits may be in the main chain or backbone of the polymer, but they mayalso be present in grafted or pendent chains. In the main chain, thesiloxane units may be in the form of segments as described above. In thependent or grafted chains, the siloxane units may appear individually orin segments.

According to the invention, the preferred siloxane-based polyamides are:

polyamides of formula (III) in which m is from 15 to 50;

mixtures of two or more polyamides in which at least one polyamide has avalue of m in the range from 15 to 50 and at least one polyamide has avalue of m in the range from 30 to 50;

polymers of formula (V) with m₁ chosen in the range from 15 to 50 and m₂chosen in the range from 30 to 500 with the portion corresponding to m₁representing 1% to 99% by weight of the total weight of the polyamideand the portion corresponding to m₂ representing 1% to 99% by weight ofthe total weight of the polyamide;

mixtures of polyamide of formula (III) combining

1) 80% to 99% by weight of a polyamide in which n is equal to 2 to 10and in particular 3 to 6, and

2) 1% to 20% of a polyamide in which n is in the range from 5 to 500 andin particular from 6 to 100;

polyamides corresponding to formula (VI) in which at least one of thegroups Y and Y¹ contains at least one hydroxyl substituent;

polyamides of formula (III) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polyamides of formula (III) in which X represents —(CH₂)₃— or —(CH₂)₁₀;and

polyamides of formula (III) in which the polyamides end with amonofunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

According to the invention, the ends of the polymer chains may end with:

a C₁ to C₅₀ alkyl ester group by introducing a C₁ to C₅₀ monoalcoholduring the synthesis,

a C₁ to C₅₀ alkylamide group by taking as stopping group a monoacid ifthe silicone is α,ω-diaminated, or a monoamine if the silicone is anα,ω-dicarboxylic acid.

According to one embodiment variant of the invention, it is possible touse a copolymer of silicone polyamide and of hydrocarbon-basedpolyamide, i.e. a copolymer comprising moieties of formula (III) or (IV)and hydrocarbon-based polyamide moieties. In this case, thepolyamide-silicone moieties may be arranged at the ends of thehydrocarbon-based polyamide.

Polyamide-based gelling agents containing silicones may be produced bysilylic amidation of polyamides based on fatty acid dimer. This approachinvolves the reaction of free acid sites existing on a polyamide as endsites, with oligosiloxane-monoamines and/or oligosiloxane-diamines(amidation reaction), or alternatively with oligosiloxane alcohols oroligosiloxane diols (esterification reaction). The esterificationreaction requires the presence of acid catalysts, as is known in theart. It is desirable for the polyamide containing free acid sites, usedfor the amidation or esterification reaction, to have a relatively highnumber of acid end groups (for example polyamides with high acidnumbers, for example from 15 to 20).

For the amidation of the free acid sites of the hydrocarbon-basedpolyamides, siloxane diamines with 1 to 300, more particularly 2 to 50and better still 2, 6, 9.5, 12, 13.5, 23 or 31 siloxane groups, may beused for the reaction with hydrocarbon-based polyamides based on fattyacid dimers. Siloxane diamines containing 13.5 siloxane groups arepreferred, and the best results are obtained with the siloxane diaminecontaining 13.5 siloxane groups and polyamides containing high numbersof carboxylic acid end groups.

The reactions may be carried out in xylene to extract the water producedfrom the solution by azeotropic distillation, or at higher temperatures(about 180 to 200° C.) without solvent. Typically, the efficacy of theamidation and the reaction rates decrease when the siloxane diamine islonger, that is to say when the number of siloxane groups is higher.Free amine sites may be blocked after the initial amidation reaction ofthe diaminosiloxanes by reacting them either with a siloxane acid, orwith an organic acid such as benzoic acid.

For the esterification of the free acid sites on the polyamides, thismay be performed in boiling xylene with about 1% by weight, relative tothe total weight of the reagents, of para-toluenesulphonic acid ascatalyst.

These reactions carried out on the carboxylic acid end groups of thepolyamide lead to the incorporation of silicone moieties only at theends of the polymer chain.

It is also possible to prepare a copolymer of polyamide-silicone, usinga polyamide containing free amine groups, by amidation reaction with asiloxane containing an acid group.

It is also possible to prepare a gelling agent based on a copolymerbetween a hydrocarbon-based polyamide and a silicone polyamide, bytransamidation of a polyamide having, for example, an ethylenediamineconstituent, with an oligosiloxane-α,ω-diamine, at high temperature (forexample 200 to 300° C.), to carry out a transamidation such that theethylenediamine component of the original polyamide is replaced with theoligosiloxane diamine.

The copolymer of hydrocarbon-based polyamide and of polyamide-siliconemay also be a graft copolymer comprising a hydrocarbon-based polyamidebackbone with pendent oligosiloxane groups.

This may be obtained, for example:

by hydrosilylation of unsaturated bonds in polyamides based on fattyacid dimers;

by silylation of the amide groups of a polyamide; or

by silylation of unsaturated polyamides by means of an oxidation, thatis to say by oxidizing the unsaturated groups into alcohols or diols, toform hydroxyl groups that are reacted with siloxane carboxylic acids orsiloxane alcohols. The olefinic sites of the unsaturated polyamides mayalso be epoxidized and the epoxy groups may then be reacted withsiloxane amines or siloxane alcohols.

According to a second embodiment of the invention, the gelling agentconsists of a homopolymer or a copolymer comprising urethane or ureagroups.

As previously, the polymer may comprise polyorganosiloxane moietiescontaining two or more urethane and/or urea groups, either in thebackbone of the polymer or on side chains or as pendent groups.

The polymers comprising at least two urethane and/or urea groups in thebackbone may be polymers comprising at least one moiety corresponding tothe following formula:

in which R¹, R², R³, R⁴, X, Y, m and n have the meanings given above forformula (I), and U represents —O— or —NH—, such that:

corresponds to a urethane or urea group.

In this formula (VIII), Y may be a linear or branched C₁ to C₄₀ alkylenegroup, optionally substituted with a C₁ to C₁₅ alkyl group or a C₅ toC₁₀ aryl group. Preferably, a —(CH₂)₆— group is used.

Y may also represent a C₅ to C₁₂ cycloaliphatic or aromatic group thatmay be substituted with a C₁ to C₁₅ alkyl group or a C₅ to C₁₀ arylgroup, for example a radical chosen from the methylene-4,4-biscyclohexylradical, the radical derived from isophorone diisocyanate, 2,4- and2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4′-biphenylenemethane.Generally, it is preferred for Y to represent a linear or branched C₁ toC₄₀ alkylene radical or a C₄ to C₁₂ cycloalkylene radical.

Y may also represent a polyurethane or polyurea block corresponding tothe condensation of several diisocyanate molecules with one or moremolecules of coupling agents of the diol or diamine type. In this case,Y comprises several urethane or urea groups in the alkylene chain.

It may correspond to the formula:

in which B¹ is a group chosen from the groups given above for Y, U is—O— or —NH— and B² is chosen from:

linear or branched C₁ to C₄₀ alkylene groups, which can optionally bearan ionizable group such as a carboxylic acid or sulphonic acid group, ora neutralizable or quaternizable tertiary amine group,

C₅ to C₁₂ cycloalkylene groups, optionally bearing alkyl substituents,for example one to three methyl or ethyl groups, or alkylenesubstituents, for example the diol radical: cyclohexanedimethanol,

phenylene groups that may optionally bear C₁ to C₃ alkyl substituents,and

groups of formula:

in which T is a hydrocarbon-based trivalent radical possibly containingone or more heteroatoms such as oxygen, sulphur and nitrogen and R⁵ is apolyorganosiloxane chain or a linear or branched C₁ to C₅₀ alkyl chain.

T can represent, for example:

with w being an integer ranging from 1 to 10 and R⁵ being apolyorganosiloxane chain.

When Y is a linear or branched C₁ to C₄₀ alkylene group, the —(CH₂)₂—and —(CH₂)₆— groups are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to5, preferably from 0 to 3 and more preferably equal to 1 or 2.

Preferably, B² is a linear or branched C₁ to C₄₀ alkylene group, inparticular —(CH₂)₂— or —(CH₂)₆— or the group:

with R⁵ being a polyorganosiloxane chain.

As previously, the polymer constituting the gelling agent may be formedfrom silicone urethane and/or silicone urea moieties of different lengthand/or constitution, and may be in the form of block or randomcopolymers.

According to the invention, the silicone may also comprise urethaneand/or urea groups no longer in the backbone but as side branches.

In this case, the polymer may comprise at least one moiety of formula:

in which R¹, R², R³, m₁ and m₂ have the meanings given above for formula(I),

U represents O or NH,

R²³ represents a C₁ to C₄₀ alkylene group, optionally comprising one ormore heteroatoms chosen from O and N, or a phenylene group, and

R²⁴ is chosen from linear, branched or cyclic, saturated or unsaturatedC₁ to C₅₀ alkyl groups, and phenyl groups optionally substituted withone to three C₁ to C₃ alkyl groups.

The polymers comprising at least one moiety of formula (X) containsiloxane units and urea or urethane groups, and they may be used asgelling agents in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group perbranch or may have branches containing two urea or urethane groups, oralternatively they may contain a mixture of branches containing one ureaor urethane group and branches containing two urea or urethane groups.

They may be obtained from branched polysiloxanes, comprising one or twoamino groups per branch, by reacting these polysiloxanes withmonoisocyanates.

As examples of starting polymers of this type containing amino anddiamino branches, mention may be made of the polymers corresponding tothe following formulae:

In these formulae, the symbol “/” indicates that the segments may be ofdifferent lengths and in a random order, and R represents a linearaliphatic group preferably containing 1 to 6 carbon atoms and betterstill 1 to 3 carbon atoms.

Such polymers containing branching may be formed by reacting a siloxanepolymer, containing at least three amino groups per polymer molecule,with a compound containing only one monofunctional group (for example anacid, an isocyanate or an isothiocyanate) to react this monofunctionalgroup with one of the amino groups and to form the groups capable ofestablishing hydrogen interactions. The amino groups may be on sidechains extending from the main chain of the siloxane polymer, such thatthe groups capable of establishing hydrogen interactions are formed onthese side chains, or alternatively the amino groups may be at the endsof the main chain, such that the groups capable of hydrogen interactionwill be end groups of the polymer.

As a procedure for forming a polymer containing siloxane moieties andgroups capable of establishing hydrogen interactions, mention may bemade of the reaction of a siloxane diamine and of a diisocyanate in asilicone solvent so as to provide a gel directly. The reaction may beperformed in a silicone fluid, the resulting product being dissolved inthe silicone fluid, at high temperature, the temperature of the systemthen being reduced to form the gel.

The polymers that are preferred for incorporation into the compositionsaccording to the present invention are siloxane-urea copolymers that arelinear and that contain urea groups as groups capable of establishinghydrogen interactions in the backbone of the polymer.

As an illustration of a polysiloxane ending with four urea groups,mention may be made of the polymer of formula:

in which Ph is a phenyl group and n is a number from 0 to 300, inparticular from 0 to 100, for example 50.

This polymer is obtained by reacting the following polysiloxanecontaining amino groups:

with phenyl isocyanate.

The polymers of formula (VIII) comprising urea or urethane groups in thechain of the silicone polymer may be obtained by reaction between asilicone containing α,ω-NH₂ or —OH end groups, of formula:

in which m, R¹, R², R³, R⁴ and X are as defined for formula (I), and adiisocyanate OCN—Y—NCO in which Y has the meaning given in formula (I);and optionally a diol or diamine coupling agent of formula H₂N—B²—NH₂ orHO—B²—OH, in which B² is as defined in formula (IX).

According to the stoichiometric proportions between the two reagents,diisocyanate and coupling agent, Y may have the formula (IX) with dequal to 0 or d equal to 1 to 5.

As in the case of the polyamide silicones of formula (II) or (III), itis possible to use in the invention polyurethane or polyurea siliconescontaining moieties of different length and structure, in particularmoieties whose lengths differ by the number of silicone moieties. Inthis case, the copolymer may correspond, for example, to the formula:

in which R¹, R², R³, R⁴, X, Y and U are as defined for formula (VIII)and m₁, m₂, n and p are as defined for formula (V).

Branched polyurethane or polyurea silicones may also be obtained using,instead of the diisocyanate OCN—Y—NCO, a triisocyanate of formula:

A polyurethane or polyurea silicone containing branches comprising anorganosiloxane chain with groups capable of establishing hydrogeninteractions is thus obtained. Such a polymer comprises, for example, amoiety corresponding to the formula:

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹¹ to R¹⁸ are groups chosen from the samegroup as R¹ to R⁴, m₁ and m₂ are numbers in the range from 1 to 1 000,and p is an integer ranging from 2 to 500.

As in the case of the polyamides, this copolymer can also comprisepolyurethane silicone moieties without branching.

In this second embodiment of the invention, the siloxane-based polyureasand polyurethanes that are preferred are:

polymers of formula (VIII) in which m is from 15 to 50;

mixtures of two or more polymers in which at least one polymer has avalue of m in the range from 15 to 50 and at least one polymer has avalue of m in the range from 30 to 50;

polymers of formula (XII) with m₁ chosen in the range from 15 to 50 andm₂ chosen in the range from 30 to 500 with the portion corresponding tom₁ representing 1% to 99% by weight of the total weight of the polymerand the portion corresponding to m₂ representing 1% to 99% by weight ofthe total weight of the polymer;

mixtures of polymer of formula (VIII) combining

1) 80% to 99% by weight of a polymer in which n is equal to 2 to 10 andin particular 3 to 6, and

2) 1% to 20% of a polymer in which n is in the range from 5 to 500 andin particular from 6 to 100,

copolymers comprising two moieties of formula (VIII) in which at leastone of the groups Y contains at least one hydroxyl substituent;

polymers of formula (VIII) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polymers of formula (VIII) in which X represents —(CH₂)₃— or —(CH₂)₁₀—;and

polymers of formula (VIII) in which the polymers end with amonofunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

As in the case of the polyamides, copolymers of polyurethane or polyureasilicone and of hydrocarbon-based polyurethane or polyurea may be usedin the invention by performing the reaction for synthesizing the polymerin the presence of an α,ω-difunctional block of non-silicone nature, forexample a polyester, a polyether or a polyolefin.

As has been seen previously, gelling agents consisting of homopolymersor copolymers of the invention may contain siloxane moieties in the mainchain of the polymer and groups capable of establishing hydrogeninteractions, either in the main chain of the polymer or at the endsthereof, or on side chains or branches of the main chain. This maycorrespond to the following five arrangements:

in which the continuous line is the main chain of the siloxane polymerand the squares represent the groups capable of establishing hydrogeninteractions.

In case (1), the groups capable of establishing hydrogen interactionsare arranged at the ends of the main chain. In case (2), two groupscapable of establishing hydrogen interactions are arranged at each ofthe ends of the main chain.

In case (3), the groups capable of establishing hydrogen interactionsare arranged within the main chain in repeating moieties.

In cases (4) and (5), these are copolymers in which the groups capableof establishing hydrogen interactions are arranged on branches of themain chain of a first series of moieties that are copolymerized withmoieties not comprising groups capable of establishing hydrogeninteractions. The values n, x and y are such that the polymer has thedesired properties in terms of an agent for gelling fatty phases basedon silicone oil.

According to the invention, the structuring of the liquid fatty phasecontaining at least one silicone oil, is obtained with the aid of one ormore of the polymers mentioned above, in combination with one or morenon-polymeric organogelling agents.

As examples of polymers that may be used, mention may be made of thesilicone polyamides obtained in accordance with Examples 1 and 2 ofdocument U.S. Pat. No. 5,981,680.

The polymers and copolymers used in the gelling system of thecomposition of the invention advantageously have a softening point from40 to 190° C. Preferably, they have a softening point ranging from 50 to140° C. and better still from 70° C. to 120° C. This softening point islower than that of the known structuring polymers, which facilitates theuse of the polymers that are the subject of the invention, allows theuse of volatile oils and limits the deteriorations of the liquid fattyphase.

They have good solubility in silicone oils and produce macroscopicallyhomogeneous compositions. Preferably, they have an average molecularmass from 500 to 200 000, for example from 80 000 to 200 000, preferablyfrom 2 000 to 30 000.

Non-Polymeric Organogelling Agent

The composition according to the invention contains one or moreorganogelling agents. This or these organogelling agent(s) make itpossible to reinforce the mechanical properties of the composition, inparticular the properties of resistance to shearing when it is in theform of a stick. This reinforcement results in a stick which isresistant to the shearing produced during the application of thecomposition to the lips or the skin, but also to the superficial bodygrowths. Thus, it is possible to manufacture a lipstick having a stickdiameter of 12.7 mm, which diameter corresponds to that customarily usedin conventional lipsticks.

According to the invention, the composition comprises at least oneorganogelling agent. An organogelling agent is defined here ascomprising a non-polymeric organic compound whose molecules may becapable of establishing, with each other, at least one physicalinteraction leading to self-aggregation of the molecules with formationof a three-dimensional macromolecular network which may be responsiblefor the gelling of the liquid fatty phase. The network can result fromthe formation of a network of fibrils (due to the stacking oraggregation of the organic gelling molecules), immobilizing themolecules of the liquid fatty phase. Depending on the nature of theorganogelling agent, the interconnected fibrils have variable sizeswhich may range from a few nanometres to 1 μm or even severalmicrometres. These fibrils can occasionally combine to form ribbons orcolumns.

The term “gelling” means a thickening of the medium which may lead to agelatinous consistency and even to a rigid, solid consistency which doesnot run under its own weight. The capacity to form this network offibrils, and thus the gelling, depends on the nature (or the chemicalcategory) of the organogelling agent, the nature of the substituentscarried by its molecules for a given chemical category, and the natureof the liquid fatty phase. For example, this gelling is reversible underthe action of an external stimulus such as temperature.

The physical interactions are diverse but may exclude cocrystallization.These physical interactions are for example interactions chosen fromself-complementary hydrogen interactions, π interactions betweenunsaturated nuclei, dipolar interactions, and coordination bonds withorganometallic derivatives. The establishment of these interactions canoften be promoted by the architecture of the molecule, for example bynuclei, unsaturations, and the presence of asymmetric carbon. Ingeneral, each molecule of an organogelling agent can establish severaltypes of physical interaction with a neighbouring molecule. Thus, in oneembodiment, the molecules of the organogelling agent according to theinvention may comprise at least one group capable of establishing ahydrogen bond, for example at least two groups capable of establishing ahydrogen bond; at least one aromatic nucleus, for example at least twoaromatic nuclei; at least one bond with ethylenic unsaturation; and/orat least one asymmetric carbon. The groups capable of forming a hydrogenbond may be chosen, for example, from the hydroxyl, carbonyl, amine,carboxylic acid, amide, benzyl, sulphonamide, carbamate, thiocarbamate,urea, thiourea, oxamido, guanidino and biguanidino groups.

The organogelling agents of the invention may be soluble in the liquidfatty phase at room temperature and at atmospheric pressure. They may besolid or liquid at room temperature and at atmospheric pressure.

Organogelling agents which may be used in the invention are, forexample, those described in the document “Specialist Surfactants”published by D. Robb, 1997, pp. 209-263, chapter 8, by P. Terech [12],and the documents FR-A-2 796 276 [13] and FR-A-2 811 552 [14]. Theorganogelling agents described in these documents are, for example,chosen from:

hydroxylated fatty carboxylic acids having a linear or branched,aliphatic carbon chain containing, in one embodiment, at least 8 carbonatoms such as at least 12 carbon atoms, for example 12-hydroxystearicacid and 12-hydroxyoleic acid, and their salts such as the alkali metalsalts (in particular the Li, Na and K salts) and the alkaline-earthmetal salts (for example the magnesium salts) or esters thereofresulting from esterification with a monoalcohol or a polyol having asaturated or unsaturated, linear or cyclic chain of 1 to 6 carbon atoms;

amides of carboxylic acids such as tricarboxylic acids, for examplecyclohexanetricarboxamides (see [13]), these amides corresponding, forexample, to the formula (XV) given below;

amides or esters of amino acids, for example esters of alanine andamides of valine (such as those described in the book “SpecialistSurfactants”) [12];

amides of N-acylamino acids, for example the diamides resulting from theaction of an N-acylamino acid with amines containing from 1 to 22 carbonatoms, such as those described in WO-93/23008 [15], for exampleN-acylglutamides in which the acyl group is a C₈ to C₂₂ alkyl chain, andthe dibutylamide of N-laurylglutamic acid, such as the product sold ormanufactured by the company AJINOMOTO under the name GP-1;

diamides having hydrocarbon chains each containing from 1 to 22 carbonatoms, for example from 6 to 18 carbon atoms, these hydrocarbon chainsbeing optionally substituted with ester, urea or fluoro groups (see[14]), these diamides being for example those of formula (XIV) givenbelow; and such as those resulting from the reaction ofdiaminocyclohexane, for example trans-diaminocyclohexane, and of an acidchloride;

amides or amines of steroids, such as those of deoxycholic, cholic,apocholic or lithocholic acids, and salts thereof, for exampleD-17,17-dipropyl-17a-aza-5α-homoandrostan-3β-ol or D-17,17-dipropyl-17a-aza-5α-homoandrostan-3β-ol 17a-oxy;

compounds containing several aromatic nuclei (2 or 3), such as theanthrylic derivatives comprising at least two alkyl chains containingfrom 8 to 30 carbon atoms, for example 2,3-bis(n-decyloxy)anthracene or2,3-bis(n-decyloxy)anthraquinone, or comprising a steroid group, forexample cholesteryl 4-(2-anthryloxy)butanoate or cholesterylanthraquinone-2-carboxylate and derivatives thereof;

azobenzene steroids such as those described in the book “SpecialistSurfactants” [12];

organometallic compounds, for example mononuclear copper β-diketonate(the octasubstituted copper complex of bis(3,4-nonyloxybenzoyl)methane),binuclear copper tetracarboxylates or Zn (II) complexes oftrisubstituted (para-carboxyphenyl)porphyrine;

surfactants in salt form comprising at least two linear or branchedalkyl chains, such as alkali metal or aluminium alkyl phosphatescomprising two alkyl chains containing from 8 to 30 carbon atoms, forexample the aluminium salt of hexadecyl phosphate (C₁₆DP—Al) orbis(2-ethylhexyl)phosphate and alkali metal (Na) salts thereof,bis(2-ethylhexyl) sulphosuccinate and alkali metal (Na) salts thereof;

benzylidene sorbitols or alditols and derivatives thereof, for example1,3:2,4-di-o-benzylidene-D-sorbitol;

cyclodipeptides which are cyclic condensates of two amino acids such asthose described in the book “Specialist Surfactants” [12];

cyclic compounds or alkylene compounds comprising two urea or urethanegroups such as dialkylurea cyclohexane, having for example the formula(XVI) given below;

alkylaryl derivatives of cyclohexanol in which the alkyl chain is linearor branched and comprises from 1 to 22 carbon atoms, and the aryl partis for example a phenyl group, these derivatives being for example4-tert-butyl-1-phenylcyclohexanol;

calixarenes such as those mentioned in the book “Specialist Surfactants”[12];

combinations of 2,4,6-triaminopyrimidines which are substituted with analkyl chain and of dialkylbarbituric acid, the alkyl chains thereofbeing linear or branched and comprising from 1 to 22 carbon atoms;

the organogelling agents defined in the document WO-A-01/07007 [16]corresponding to the general formula (XVII):Q-O—W—(CHOH)—W¹—O-Q¹  (XVII)

in which W and W¹, which may be identical or different, are chosen from—CH₂— and —CO—, and in which Q and Q¹, which may be identical ordifferent, are a hydrocarbon chain chosen from saturated or unsaturated,linear or branched hydrocarbon chains containing at least 6 carbonatoms, and in which s is an integer from 2 to 4; such as the compoundsin which W═W¹ 50 —CH₂— and s=2 and the compounds in which W═W¹═—CO— ands=4;

gluconamide derivatives such as those described in the article R. J. H.Hafkamp, Chem. Commun., (1997), pages 545-46 [17], and in the article J.Org. Chem., vol. 64, No. 2; 412-26 (1999) [18], corresponding to theformula (XVIII):R²⁵—NH—CO—[CH(OH)]₄—CH₂R²⁶  (XVIII)

in which R²⁵ is a hydrocarbon chain chosen from saturated orunsaturated, linear, branched and cyclic hydrocarbon chains having from1 to 30 carbon atoms, for example octyl, it being possible for thishydrocarbon chain to optionally comprise at least one heteroatom such asN, O and S, and in which R²⁶ represents —O—CO—R²⁷ or —O—R²⁷ with R²⁷being chosen from linear and branched alkyl chains containing from 1 to20 carbon atoms, C₅-C₈ cycloaliphatic chains and aromatic chains, C₅-C₈heterocycles comprising N, O or S atoms, and for example the compoundsin which R²⁶ is a saturated or unsaturated C₅-C₈ heterocycle comprisingan N, O or S atom such that R²⁶ represents the imidazolyl group,

cyclic ether derivatives of the compounds of formula (XVIII) having theformula (XIX):

in which R²⁵ and R²⁶ have the same meaning as in formula (XVIII);

provided that R²⁵ and R²⁶ are such that they allow the gelling of theliquid fatty phase;

diamide, diurea or diurethane derivatives of amino acids such as:

a) the bisoxalylamides of amino acids cited in the article by M. Jokic,J. Chem. Soc., Chem. Commun., pages 1723-24 (1995) [19], of formula:HOCO—CH(R²⁸)—NH—CO—CO—NH—CH(R²⁹)—COOH  (XX)

-   -   in which R²⁸ and R²⁹, which may be identical or different, are a        characteristic group of the amino acid, chosen for example from:        —CH₂—CH(CH₃)₂;—C₆H₅;—CH₂—C₆H₅;—CH(CH₃)₂;

b) the amide and urea derivatives of a lysine ester such as thosementioned in the article by K. Hanabusa, Chemistry Letters, pp. 1070-71,2000 [20], such as the ethyl or methyl ester ofN^(ε)-lauroyl-N^(α)-stearylaminocarbonyl-L-lysine and derivatives havingthe formula:C₁₁—H₂₃—CO—NH—(CH₂)₄—CH(COOR³⁰)—NH—CO—R³¹

in which R³⁰═—CH₃ or —C₂H₅ and R³¹═—NH—(CH₂)₁₇—CH₃ or —NH—(CH₂)_(n)—CH₃with n=1 to 30.

c) diamide derivatives of benzenedicarboxylic acids and of valine suchas those mentioned in the article by K. Hanabusa, Chemistry Letters, pp.767-8, 1999 [21], corresponding for example to the formulae:

in which -L-Val- represents:—NH—CH [CH(CH₃)₂)]—CO—;

monoalkyloxamides such as those described by X. Luo, Chem. Commun., pp.2091-92, 2000 [22], for example of formula:R³²—NH—CO—CO—NH—R³³

in which R³² and R³³, which may be identical or different, are ahydrocarbon chain chosen from saturated or unsaturated, linear, branchedand cyclic hydrocarbon chains having from 1 to 30 carbon atoms; andwhich may contain one or more heteroatoms such as O, N and S;

bolaamphiphiles with a 1-glucosamide head such asN,N′-bis(β-D-glucopyranosyl)-n-alkane-1-dicarboxamide, such as thecompounds mentioned in the article by T. Shimizu, J. Am. Chem. Soc.,119, pp. 2812-18, 1997 [23], corresponding to the formula (XXI):

in which n is an integer from 2 to 30, R³⁴ is —H or —CO—R³⁵ in which R³⁵is a C₁-C₂₀ alkyl group, for example the compound in which R³⁴represents —CO—CH₃;

bolaamphiphilic amides derived from amido acids mentioned by K.Hanabusa, Adv. Mater., 9, No. 14, 1997, pp. 1095-1097 [24],corresponding to the formulae:

2-alkyl-2-ammoniumisobutyl acetate p-toluenesulphonate salts such asthose described by K. Hanabusa, Colloïd Polym. Sci., 276, pp. 252-59,1998 [25], corresponding to the formula (XXII):p-CH₃—C₆H₄—SO₃ ⁻⁺H₃N—CH(R³⁷)—CO—OR³⁸  (XXII)

in which R³⁷ represents:

R³⁸ represents:

fatty esters of cellobiose such as those mentioned in WO-A-00/61080 [26]and WO-A-00/61081 [27] of formula (XXIII):

in which R³⁹═—CO—R⁴⁰ and R⁴⁰ represents an alkyl or alkylene group of 5to 12 carbon atoms;

the organogelling agents having two urea groups and two carbamate groupsmentioned in U.S. Pat. No. 6,156,325 [28] of formula (XXIV):

in which R⁴¹ is an alkyl group of 4 to 42 carbon atoms optionallycontaining oxygen atoms, and R⁴² and R⁴³, which may be identical ordifferent, represent C₂ to C₂₀ alkylene, C₅ to C₁₀ cycloalkylene or C₅to C₁₀ cycloarylene groups;

diamides of formula (XXV) or (XXVI):R⁴⁴—X—CO—NH—R⁴⁵—NH—CO—X—R⁴⁴  (XXV)orR⁴⁴—CO—NH—R⁴⁵—NH—CO—R⁴⁴  (XXVI)

in which the groups R⁴⁴, which may be identical or different, representa saturated or unsaturated, linear or branched C₈-C₆₀ hydrocarbon chain,the group(s) R⁴⁴ optionally comprising a hydroxyl group or at least oneheteroatom such as N, O, S or Si, R⁴⁵ is a hydrocarbon-based groupchosen from linear, branched and cyclic C₁ to C₅₀ groups and C₅ to C₈arylene groups optionally substituted with one or more C₁-C₄ alkylgroups, and X represents —O— or —NH—.

It is also possible to use mixtures of the various organogelling agentsdescribed above.

According to one embodiment, the organogelling agent is chosen fromamides of amino acids such as N-acylamino acids andcyclohexanetricarboxamides, and mixtures thereof.

Organogelling Agents of Formula (XIV)

According to the invention, the organogelling agent may be a compound offormula (XIV) below:R⁴⁶—CO—NH-A-NH—CO—R⁴⁷  (XIV)

in which R⁴⁶ and R⁴⁷, which may be identical or different, represent ahydrogen atom or a hydrocarbon chain chosen from saturated andunsaturated, linear, branched and cyclic hydrocarbon chains containingfrom 1 to 22 carbon atoms, for example from 6 to 18 carbon atoms, inparticular 10 to 14 carbon atoms, optionally substituted with at leastone group chosen from aryl (—C₆H₅), ester (—COOR⁴⁸ with R⁴⁸ being analkyl group of 2 to 12 carbon atoms), amide (—CONHR⁴⁸ with R⁴⁸ asdefined above), urethane (—OCONHR⁴⁸ with R⁴⁸ as defined above), and urea(—NHCONHR⁴⁸ with R⁴⁸ as defined above) groups; and/or optionallycontaining from 1 to 3 heteroatoms chosen from O, S and N; and/oroptionally substituted with 1 to 4 halogen atoms, in particular fluorineatoms, and/or 1 to 3 hydroxyl radicals,

provided that R⁴⁶ and R⁴⁷ are not both a hydrogen atom, and

A is chosen from saturated and unsaturated, linear, cyclic and branchedhydrocarbon chains containing from 1 to 18 carbon atoms, for examplefrom 2 to 12 carbon atoms, in particular from 4 to 12 carbon atoms,optionally substituted with at least one group chosen from aryl (—C₆H₅),ester (—COOR⁴⁸), amide (—CONHR⁴⁸), urethane (—OCONHR⁴⁸) and urea(—NHCONHR⁴⁸) groups; and/or optionally containing from 1 to 3heteroatoms chosen from O, S and N; and/or optionally substituted with 1to 4 halogen atoms, such as fluorine atoms, and/or 1 to 3 hydroxylradicals.

In formula (XIV), the expression “unsaturated hydrocarbon chain” means achain which comprises at least one C═C double bond or at least one C≡Ctriple bond, it being possible for the chain to be also optionallysubstituted with at least one group chosen from aryl, ester, amide,urethane and urea groups; and/or to optionally comprise at least oneheteroatom chosen from O, S and N; and/or to be optionally substitutedwith at least one fluorine atom and/or one hydroxyl radical. Theexpression “hydrocarbon chain comprising an oxygen, sulphur or nitrogenatom” in formula (XIV) includes in particular a hydrocarbon chaincomprising a carbonyl (C═O), amine (—NH₂ or —NH—), thiol (—SH),thioether or ether group.

The compounds correspond, for example, to formula (XIV) in which:

1) —A is chosen from saturated and unsaturated, but non-aromatic,optionally branched hydrocarbon nuclei containing from 4 to 12 carbonatoms, for example from 5 to 7 carbon atoms, optionally substituted withthe substituents mentioned above and/or optionally comprising at leastone heteroatom and/or being optionally substituted with at least onehalogen and/or one hydroxyl radical;

-   -   R⁴⁶ and R⁴⁷, which may be identical or different, are chosen        from a hydrogen atom and hydrocarbon chains chosen from        saturated and unsaturated, linear, branched and cyclic chains        containing from 10 to 16 carbon atoms, for example from 12 to 14        carbon atoms, in particular a saturated linear hydrocarbon        chain; or

2) —A is a saturated hydrocarbon chain chosen from saturated, linear andbranched hydrocarbon chains containing from 2 to 18 carbon atoms, forexample 3 to 12 carbon atoms, optionally substituted with thesubstituents mentioned above, and/or optionally comprising at least oneheteroatom and/or being optionally substituted with at least one halogenand/or one hydroxyl radical;

-   -   R⁴⁶ and R⁴⁷, which may be identical or different, are chosen        from a hydrogen atom and a hydrocarbon chain chosen from        saturated and unsaturated, linear, branched and cyclic        hydrocarbon chains such as saturated linear hydrocarbon chains        containing from 10 to 20 carbon atoms, for example from 11 to 18        carbon atoms, and in particular 16 carbon atoms; or        alternatively

3) —A is chosen from aryl and aralkyl nuclei containing from 4 to 12carbon atoms, for example from 5 to 8 carbon atoms, optionallysubstituted with the substituents mentioned above and/or optionallycomprising at least one heteroatom and/or optionally substituted with atleast one halogen and/or one hydroxyl radical;

-   -   R⁴⁶ and R⁴⁷, which may be identical or different, are chosen        from a hydrogen atom and hydrocarbon chains chosen from        saturated and unsaturated, linear, branched and cyclic        hydrocarbon chains, for example a saturated linear hydrocarbon        chain containing from 6 to 18 carbon atoms, for example from 10        to 16 carbon atoms.

A may be for example a divalent radical such as cyclohexylene, ethylene,propylene, isopropylene, butylene, isobutylene, pentylene, hexylene,dodecylene, dodecanylene, benzylene, phenylene, methylphenylene,bisphenylene or naphthalene.

The radicals R⁴⁶ and R⁴⁷ may be chosen, independently of each other,from pentyl, hexyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, 3-dodecyloxypropionyl, 3-octadecyloxypropionyl,3-dodecyloxypentyl, 3-octadecyloxypentyl and 11-hydroxyheptadecylradicals.

In one embodiment, R⁴⁶ and R⁴⁷ are identical.

When A is cyclic, the radicals R⁴⁶—CO—NH and R⁴⁷—CO—NH— may be in theortho, meta or para position. Furthermore, they may be in the cis ortrans position relative to each other.

In one embodiment, the compounds of formula (XIV) are a mixture of cisand trans compounds.

The compounds of formula (XIV) may be chosen from the compoundscorresponding to one of the following formulae:

in which R⁴⁶ and R⁴⁷ are as defined above.

Among the compounds which may be used as organogelling agents in thecomposition of the invention, the following compounds may be mentioned:

N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane, in particular in the transform (compound of formula (XIV) with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalentradical 1,2-cyclohexylene, also known as(2-dodecanoylaminocyclohexyl)dodecanamide). This compound is describedin particular by Hanabusa K.; Angew. Chem., 108, 1997, 17, pages2086-2088 [29];

N,N′-bis(dodecanoyl)-1,3-diaminocyclohexane, in particular in the transform (compound of formula (XIV) with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalentradical 1,3-cyclohexylene, also known as(3-dodecanoylaminocyclohexyl)dodecanamide),

N,N′-bis(dodecanoyl)-1,4-diaminocyclohexane, in particular in the transform (compound of formula (XIV) with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalentradical 1,4-cyclohexylene, also known as(4-dodecanoylaminocyclohexyl)dodecanamide),

N,N′-bis(dodecanoyl)-1,2-ethylenediamine, (compound of formula (XIV)with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalent radical 1,2-ethylene, alsoknown as (2-dodecanoylaminoethyl)dodecanamide),

N,N′-bis(dodecanoyl)-1-methyl-1,2-ethylenediamine, (compound of formula(XIV) with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalent radical1-methyl-1,2-ethylene, also known as(2-dodecanoylamino-2-methylethyl)dodecanamide),

N,N′-bis(dodecanoyl)-1,3-diaminopropane (compound of formula (XIV) withR⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalent radical propylene, also known as(2-dodecanoylaminopropyl)dodecanamide),

N,N′-bis(dodecanoyl)-1,12-diaminododecane (compound of formula (XIV)with R⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalent radical 1,12-dodecylene, alsoknown as (2-dodecanoylaminododecyl)dodecanamide),

N,N′-bis(dodecanoyl)-3,4-diaminotoluene (compound of formula (XIV) withR⁴⁶═R⁴⁷=n-C₁₁H₂₃ and A=the divalent radical 1-methyl-3,4-phenylene, alsoknown as (2-dodecanoylamino-4-methylphenyl)dodecanamide), and

mixtures thereof.

The compounds of formula (XIV) may be prepared according to methods wellknown to persons skilled in the art.

In particular, they may be obtained by reacting a diamine H₂N-A-NH₂ withan acid chloride R⁴⁶COCl and/or R⁴⁷COCl where R⁴⁶ and R⁴⁷ have themeanings given above, in an organic solvent medium which is compatiblefor carrying out the reaction (1 mol of acid chloride is used per mol ofdiamine if it is desired to obtain a compound of formula (XIV)containing only one group R⁴⁶ other than a hydrogen atom, or 2 mol ofacid chloride R⁴⁶COCl and/or R⁴⁷COCl, if it is desired to obtain acompound of formula (XIV) in which R⁴⁶ and R⁴⁷ are different from ahydrogen atom). The reaction is preferably carried out in the presenceof a base capable of neutralizing the formation of HCl released duringthe reaction. The diamide formed is extracted from the reaction mediumaccording to extraction techniques which are well known to personsskilled in the art.

The compounds of formula (XIV) may be used, alone or in the form of amixture, in the composition of the invention.

Standard Preparation of Compounds of Formula (XIV) with R⁴⁶═R⁴⁷

The diamine and two equivalents of triethylamine are dissolved in 50 mlof tetrahydrofuran (THF). Two equivalents of acyl chloride dissolved inTHF are added and the reaction mixture is heated to the refluxingtemperature of tetrahydrofuran, while monitoring the disappearance ofthe acyl chloride by infrared spectroscopy (typically for the majorityin two hours). The precipitate is removed from the solution byfiltration, the organic phase is concentrated and a liquid/liquidextraction is carried out on the solid compound obtained. The organicphase is then dried and then concentrated and the solid product obtainedis recrystallized.

Organogelling Agents of Formula (XV):

in which the groups R⁴⁸, which are identical or different, are chosenfrom a hydrogen atom and saturated, linear and branched hydrocarbonchains, the said hydrocarbon chains containing from 1 to 6 carbon atoms,for example from 1 to 4 carbon atoms;

-   -   the groups Z, which are identical or different, each represent a        group chosen from the following groups: —CO—S—R⁴⁹; —CO—NHR⁴⁹;        —NH—COR⁴⁹ and —S—COR⁴⁹; in which the groups R⁴⁹, which may be        identical or different, are chosen from:    -   a hydrogen atom,    -   an aryl group,    -   an aralkyl group, that is to say an aryl group substituted with        a hydrocarbon chain chosen from saturated, linear and branched        hydrocarbon chains, in which the hydrocarbon chain contains from        1 to 22 carbon atoms, for example from 10 to 18 carbon atoms,        and    -   a saturated hydrocarbon chain chosen from linear, branched and        cyclic hydrocarbon chains, containing from 1 to 22 carbon atoms,        for example from 10 to 18 carbon atoms, optionally substituted        with at least one group chosen from aryl, ester, amide and        urethane groups; and/or optionally comprising at least one        heteroatom chosen from O, S and N; and/or optionally substituted        with at least one fluorine atom and/or one hydroxyl radical.

R⁴⁸ is for example a hydrogen atom.

Z is for example the group —CO—NHR⁴⁹ or —NH—COR⁴⁹.

R⁴⁹ is for example an aryl group; an aralkyl group in which the linearor branched alkyl chain contains from 12 to 16 carbon atoms; or a linearor branched C₁₁-C₁₈ alkyl group.

In one embodiment, Z is a group —CO—NHR⁴⁹ in which R⁴⁹ is chosen fromaryl groups substituted with a linear or branched C₁₁-C₁₆ alkyl chain,unsubstituted linear C₁₁ to C₁₈ alkyl chains and unsubstituted branchedC₁₁ to C₁₈ alkyl chains.

In the compounds of formula (XV), the three substituents represented byZ may be in cis-cis, cis-trans or trans-trans conformation relative toeach other. In particular, at least one of these substituents may beplaced in an equatorial position on the cyclohexane nucleus; for exampleall the substituents Z are placed in an equatorial position.

It is also possible to use, as compound of formula (XV), a mixture ofcis-cis, cis-trans and/or trans-trans compounds.

Among the compounds of formula (XV) which may be used as organogellingagent, alone or in the form of a mixture, in the composition of theinvention, the following compounds may be mentioned:

-   cis-1,3,5-tris(dodecylaminocarbonyl)cyclohexane,-   cis-1,3,5-tris(octadecylaminocarbonyl)cyclohexane,-   cis-1,3,5-tris[N-(3,7-dimethyloctyl)aminocarbonyl]-cyclohexane,-   trans-1,3,5-trimethyl-1,3,5-tris(dodecylaminocarbonyl)cyclohexane,    and-   trans-1,3,5-trimethyl-1,3,5-tris(octadecylaminocarbonyl)cyclohexane.

The compounds of formula (XV) are well known to persons skilled in theart and may be prepared by conventional methods.

It is also possible to add to the composition an organic compound asdescribed in U.S. Pat. No. 6,156,325 [28]. Such compounds include ureaurethanes having the following formula:R⁵⁰—O—CO—NH—R⁵¹—NH—CO—NH—R⁵²—NH—CO—NH—R⁵¹—NH—CO—OR⁵⁰where R⁵⁰ represents C_(n)H_(2n+1-) or C_(m)H_(2m+1)(C_(p)H_(2p)O)_(r);n represents an integer having a value of 4 to 22; m represents aninteger having a value of 1 to 18; p represents an integer having avalue of 2 to 4; and r represents an integer having a value of 1 to 10,

R⁵¹ represents:

and R⁵² represents:

As is evident from the above urea urethane formula, the alkyl groups andthe alkyl parts designated for R⁵⁰ are saturated.

Organogelling Agent of Formula (XVI)

According to the invention, the organogelling agent may be at least oneorganogelling agent of formula (XVI):R⁴⁶NHCONHANHCONHR⁴⁶  (XVI)

in which A and R⁴⁶ have the same meaning as that given for formula (XIV)given above, that is in which

-   -   the groups R⁴⁶, which may be identical or different, each        represent a hydrogen atom or a hydrocarbon chain chosen from        saturated and unsaturated, linear, branched and cyclic        hydrocarbon chains containing from 1 to 22 carbon atoms, for        example from 6 to 18 carbon atoms, optionally substituted with        at least one group chosen from aryl (—C₆H₅), ester (—COOR⁴⁸        where R⁴⁸ is as defined above), amide (—CONHR⁴⁸), urethane        (—OCONHR⁴⁸) and urea (—NHCONHR⁴⁸) groups; and/or optionally        containing from 1 to 3 heteroatoms chosen from O, S and N;        and/or optionally substituted with 1 to 4 hydrogen atoms, in        particular fluorine atoms, and/or 1 to 3 hydroxyl radicals,

provided that at least one R⁴⁶ is other than a hydrogen atom, and

-   -   A is chosen from saturated and unsaturated, linear, cyclic and        branched hydrocarbon chains containing from 1 to 18 carbon        atoms, for example from 2 to 12 carbon atoms, optionally        substituted with at least one group chosen from aryl (—C₆H₅),        ester (—COOR⁴⁸), amide (—CONHR⁴⁸), urethane (—OCONHR⁴⁸) and urea        (—NHCONHR⁴⁸) groups; and/or optionally containing from 1 to 3        heteroatoms chosen from O, S and N; and/or optionally        substituted with 1 to 4 halogen atoms such as fluorine atoms,        and/or 1 to 3 hydroxyl radicals.

According to the invention, among the organogelling agents describedabove, those which can be carried in silicone oils and considered asgelling agents for these media when they are used alone, without thepolymer of the invention, are preferred. They are the followingcompounds:

a) 12-hydroxystearic acid, its salts and its ester or amide derivativeswhich are described in the documents U.S. Pat. No. 5,480,637 [30],EP-A-616 842 [31] and EP-A-665 007 [32] as gelling agents for siliconeoils.

b) amides of tricarboxylic acids, for example their diamides asdescribed in U.S. Pat. No. 5,776,494 [33].

c) esters and amides of N-acylamino acids described in WO-A-93/23008[15] and U.S. Pat. No. 5,429,816 [34], for example N-acylglutamideswhere the acyl group is a C₈ to C₂₂, and the dibutylamide ofN-laurylglutamic acid from Ajinomoto.

d) diureas of N-acylamino acids such as the methyl or ethyl esters ofN^(ε)-lauroyl-N^(α)stearylaminocarbonyl-L-lysine and ofN^(ε)-lauroyl-N^(α)-n-butylamino-L-lysine of formulae:

These derivatives are described by K. Hanabusa, Chemistry Letters, 2000,pp. 1070-1071 [20].

e) Urethane amides of certain dipeptides such asN-benzyloxycarbonyl-L-valyl-L-valine n-octadecylamide of formula:

described by K. Hanabusa, J. Chem. Soc., Chem. Commun., 1993, pages390-92 [35].

f) Dibenzylidenesorbitol and its derivatives.

g) Sterol derivatives such as:

-   -   the lanosterol described in EP-A-1 064 925 [36],    -   dihydrolanosterol,    -   cholesterol esters such as cholesterylphenyl acetate,        cholesteryl laureate, cholesteryl cinnamate and cholesteryl        4-(2-anthryloxy)butanoate, and cholesterol esters with        azobenzene groups such as:

described by P. Terech, Chem. Rev., 97, 3133-59, 1997 [37].

h) Certains cyclodipeptides cited in the article by K. Hanabusa, J.Colloïd and Int. Sci., 224, pp. 231-44, 2000 [38], in particular:cyclo(glycyl-L-alanyl), cyclo(glycyl-L-valyl), cyclo(glycyl-L-leucyl),cyclo(glycyl-L-phenylalanyl), cyclo(L-valyl-L-leucyl),cyclo(L-leucyl-L-leucyl), cyclo(L-phenylalanyl-L-leucyl),cyclo(L-phenylalanyl-L-phenylalanyl),cyclo(L-valyl-L-γ-3,7-dimethyloctylglutamyl),cyclo(L-valyl-L-γ-2-ethylhexylglutamyl),cyclo(L-leucyl-L-γ-ethylglutamyl), cyclo(L-leucyl-L-γ-dodecylglutamyl),cyclo(L-leucyl-L-γ-3,7-dimethyloctylglutamyl),cyclo(L-leucyl-L-γ-benzylglutamyl),cyclo(L-β-butylasparaginyl-L-phenylalanyl),cyclo(L-γ-dodecylasparaginyl-L-phenylalanyl),cyclo(L-β-3,7-dimethyloctylasparaginyl-L-phenylalanyl),cyclo(L-β-2-ethylhexylasparaginyl-L-phenylalanyl),cyclo(L-β-3,5,5-trimethylhexylasparaginyl-L-phenylalanyl) andcyclo(L-β-2-ethylbutylasparaginyl-L-phenylalanyl).

i) the trans-(1R,2R)-bis(undecylcarbonylamino)-cyclohexane derivative offormula:

j) Fluorinated ethers such as those defined in U.S. Pat. No. 6,002,048[39].

k) The organogelling agents defined in WO 01/07007 [16], of generalformula (XVII) described above.

l) The bolaamphiphilic amide organogelling agents derived from aminoacids mentioned above.

m) The 2-alkyl-2-ammoniumisobutyl acetate p-toluenesulfonate salts offormula (XXII) cited above, in particular that for which R³⁷ is derivedfrom L-leucine and R³⁸ represents —(CH₂)₁₁CH₃.

n) The diamide derivatives of benzenedicarboxylic acid and of valinecited above.

o) The non-polymeric organogelling agents of formula (XXV) or (XXVI)described above.

Among the preferred organogelling agents, the ones which will be evenmore preferred are those which are compatible with silicone oils andwhich in addition possess groups which can give hydrogen interactionswith the polyorganosiloxane polymers used in the invention, that isamide, urea, urethane, ester, sulfonamide, carbamate, thiocarbamate,thiourea, oxamido, guanidino and biguanidino groups, and combinationsthereof.

In a particularly preferred manner, there will be used in accordancewith the invention:

-   -   12-hydroxystearic acid amide derivatives,    -   amides of tricarboxylic acids,    -   esters or amides of N-acylamino acids,    -   the diureas cited above,    -   urethane amides of certain dipeptides,    -   the cyclodipeptides cited above,    -   the derivatives of formula (XIV) and more particularly        trans-(1R,2R)-bis(undecylcarbonylamino)cyclohexane,    -   bolaamphipilic amide organogelling agents derived from amino        acids,    -   diamide derivatives of benzenedicarboxylic acid and of valine,        and    -   organogelling agents which are soluble in silicone oils and        which have a non-polymeric structure, defined by the formulae        XXV and XXVI given above.

According to the invention, the polymer may be combined with at leastone amphiphilic compound which is liquid at room temperature, having ahydrophilic/lipophilic balance (HLB) value of less than 12, inparticular ranging from 1 to 7, preferably from 1 to 5, and even betterfrom 3 to 5. According to the invention, it is possible to use one ormore amphiphilic compounds. The aim of these amphiphilic compounds is toreinforce the structuring properties of the polymer, to facilitate theuse of the polymer and to enhance the capacity of the stick to form adeposit.

According to the invention, the composition preferably has a hardnessranging from 20 to 2 000 gf and better still from 20 to 900 gf,particularly from 20 to 600 gf, and for example from 150 to 450 gf. Thishardness may be measured according to a method of penetration of a probeinto the said composition and in particular with the aid of a textureanalyser (for example TA-TXT2i from Rheo) equipped with an ebonitecylinder 25 mm in height and 8 mm in diameter. The hardness measurementis carried out at 20° C. at the centre of five samples of the saidcomposition. The cylinder is introduced into each sample of compositionat a pre-speed of 2 mm/s, then at a speed of 0.5 mm/s and finally at apost-speed of 2 mm/s, the total displacement being 1 mm. The recordedhardness value is that of the maximum peak. The measurement error is ±50gf.

The hardness may also be measured by the “cheese wire” method, whichconsists in cutting a tube of lipstick 12.7 mm or 8.1 mm in diameter andin measuring the hardness at 20° C., using a DFGHS 2 tensile testingmachine from the company Indelco-Chatillon, travelling at a speed of 100mm/minute. It is expressed as the shear force (expressed in gram-force)required to cut a stick under these conditions. According to thismethod, the hardness of a composition in stick form according to theinvention ranges from 30 to 300 gf, preferably from 30 to 250 gf, for astick 12.7 mm in diameter and for example from 30 to 120 gf for a stick8.1 mm in diameter.

The hardness of the composition according to the invention is such thatthe composition is self-supporting and can disintegrate easily to form asatisfactory deposit on the skin and the lips. In addition, with thishardness, the composition of the invention shows good impact strength.

According to the invention, the composition in stick form has thebehaviour of a deformable and supple elastic solid, giving noteworthyelastic softness on application. The stick compositions of the prior artdo not have this property of elasticity and suppleness.

The amphiphilic, silicone and non-silicone compound(s) which can be usedin the composition of the invention comprise a lipophilic part linked toa polar part, the lipophilic part containing a carbon chain having atleast 8 carbon atoms, in particular from 18 to 32 carbon atoms and evenbetter from 18 to 28 carbon atoms. Preferably, the polar part of this orthese amphiphilic compound(s) is the residue of a compound chosen fromalcohols and polyols having from 1 to 12 hydroxyl groups,polyoxyalkylenes containing at least two oxyalkylenated moieties andhaving from 0 to 20 oxypropylenated moieties and/or from 0 to 20oxyethylenated moieties. In particular, the amphiphilic compound is anester chosen from hydroxystearates, oleates and isostearates ofglycerol, sorbitan or methylglucose, or branched C₁₂ to C₂₆ fattyalcohols such as octyldodecanol and mixtures thereof. Among theseesters, monoesters and mixtures of mono- and diesters are preferred.

The respective amounts of lipophilic non-polymeric organogelling agentand of structuring silicone polymer and optionally of amphiphiliccompound are chosen according to the desired gel hardness and dependingon the particular application envisaged. The respective quantities ofpolymer, organogelling agent and optionally of amphiphilic compoundshould be such that they allow the production of a self-supportedcomposition, for example in the form of a disintegrable stick. Inpractice, the quantity of polymer (as active material) represents from0.5 to 80% of the total weight of the composition, and even better from5 to 40%. The quantity of amphiphilic compound represents in practicefrom 0.1% to 35% of the total weight of the composition, for examplefrom 1% to 20% and even better from 2% to 15%. The quantity oforganogelling agent represents in practice from 0.1 to 80%, preferablyfrom 0.5 to 60%, and even better from 1 to 40% and better still from 1to 15% of the total weight of the composition.

According to the invention, it is in fact preferable for the quantity oforganogelling agent to be smaller than the quantity of structuringsilicone polymer.

Generally, the silicone polymer/non-polymeric organogelling agent massratio is in the range from 20 to 0.15, preferably from 15 to 1.5.

Other Additives

The composition of the invention may also comprise any ingredientusually used in the field under consideration, and especially thosechosen from dyes that are soluble in polyols or in the fatty phase,antioxidants, essential oils, preserving agents, perfumes, liposolublepolymers, especially hydrocarbon-based liposoluble polymers such aspolyalkylenes or polyvinyl laurate, liquid-fatty-phase gelling agents,waxes, gums, resins, surfactants, for instance trioleyl phosphate,additional cosmetic or dermatological active agents such as, forexample, water, emollients, moisturizers, vitamins, liquid lanolin,essential fatty acids, lipophilic sunscreens or sunscreens that aresoluble in polyols, and mixtures thereof. The composition according tothe invention may also contain lipid vesicles of ionic and/or non-ionictype. These ingredients, besides the water, may be present in thecomposition in the usual manner in a proportion of from 0% to 20% of thetotal weight of the composition and better still from 0.1% to 10%.

In the case where the composition contains an aqueous phase, which isthe case for a simple or multiple emulsion, this aqueous phase canrepresent 0.1% to 70% of the total weight of the composition, especiallyfrom 0.5% to 40% and better still from 1% to 20%. This aqueous phase cancontain any water-miscible compound such as polyols and may beoptionally gelled with a suitable gelling agent.

Needless to say, the person skilled in the art will take care to selectthe optional additional ingredients and/or the amount thereof such thatthe advantageous properties of the composition according to theinvention are not, or are not substantially, adversely affected by theenvisaged addition.

The compositions of the invention may in particular contain one or morewaxes, for example polyethylene wax, but the use of wax is avoided if itis desired to obtain glossy, or even transparent products. Generally,the amount of wax does not exceed 20% and preferably 10%; it represents,for example, from 3% to 5% of the total weight of the composition.

The composition according to the invention may be in the form of anoptionally tinted dermatological or care composition for keratinousmaterials such as the skin, the lips and/or the superficial bodygrowths, in the form of a sun protection or care composition, especiallyin the form of a make-up-removing product in stick form. It canespecially be used as a care base for the skin, the superficial bodygrowths or the lips (lip balms, for protecting the lips against the coldand/or sunlight and/or the wind, or a care cream for the skin, the nailsor the hair).

The composition of the invention may be provided in particular in theform of a rigid gel, in particular in the form of a transparentanhydrous stick.

The composition of the invention may also be in the form of a colouredmake-up product for the skin, in particular a foundation, optionallyhaving care or treatment properties, a blusher, a face powder, aneyeshadow, a concealer product, an eyeliner or a make-up product for thebody; a lip make-up, for instance a lipstick, optionally having care ortreatment properties; a make-up for the superficial body growths, forinstance the nails or the eyelashes, in particular in the form of amascara cake, or for the eyebrows and the hair, especially in the formof a pencil. In particular, the composition of the invention may be acosmetic product containing cosmetic and/or dermatological activeagents, for instance essential oils, vitamins, moisturizers, sunscreens,cicatrizing agents and ceramides.

In the case of make-up compositions, hydrophobic or hydrophilic solidparticles may constitute the pigment(s) for making up the skin, the lipsand/or the superficial body growths.

Needless to say, the composition of the invention must be cosmeticallyor dermatologically acceptable, that is to say that it must contain anon-toxic physiologically acceptable medium that can be applied to theskin, the superficial body growths or the lips of human beings. For thepurposes of the invention, the expression “cosmetically acceptable”means a composition of pleasant appearance, odour and feel.

Moreover, the make-up or care compositions in accordance with theinvention must comprise at least 10% by mass of a non-volatile oil(silicone oil or non-silicone oil) and/or of a pasty or viscous productin order to obtain a product which is comfortable and which does notcause tightness.

The expression pasty product is understood to mean a viscous fattysubstance containing a liquid fraction and a solid fraction. For thepurposes of the invention, the expression “pasty fatty substances” meansfatty substances with a melting point ranging from 20 to 55° C. andpreferably 25 to 45° C., and/or a viscosity at 40° C. ranging from 0.1to 40 Pa·s (1 to 400 poises) and preferably 0.5 to 25 Pa·s measuredusing a Contraves TV or Rheomat 180 viscometer, equipped with a spindlerotating at 240 min⁻¹ for a power supply at 60 Hz or at 200 min⁻¹ for apower supply at 50 Hz.

A person skilled in the art can select the spindle for measuring theviscosity, from the spindles MS-r3 and MS-r4, on the basis of hisgeneral knowledge, so as to be able to measure the viscosity of thetested pasty compound.

The melting point values correspond, according to the invention, to themelting peak measured by the “Differential Scanning Calorimetry” methodwith a temperature rise of 5 or 10° C./min.

By way of example of pasty products that may be used in the invention,mention may be made of lanolins and lanolin derivatives, for instanceacetylated lanolins or oxypropylenated lanolins or isopropyl lanolate,with a viscosity of 18 to 21 Pa·s and preferably 19 to 20.5 Pa·s, and/ora melting point of 30 to 55° C., preferably 30 to 40° C., and mixturesthereof. Esters of fatty acids or of fatty alcohols may also be used,especially those containing 20 to 65 carbon atoms (melting point ofabout 20 to 35° C. and/or viscosity at 40° C. ranging from 0.1 to 40Pa·s), for instance triisostearyl citrate or cetyl citrate; arachidylpropionate; polyvinyl laurate; cholesterol esters, for instancetriglycerides of plant origin such as hydrogenated plant oils, viscouspolyesters, for instance poly(12-hydroxystearic acid) and mixturesthereof. Triglycerides of plant origin that may be used includehydrogenated castor oil derivatives, such as “THIXINR” from Rheox.

Mention may also be made of silicone-based pasty fatty substances suchas polydimethylsiloxanes (PDMSs) containing pendent chains of the alkylor alkoxy type containing from 8 to 24 carbon atoms, and having amelting point of 20-55° C., for example 20 to 40° C., for instancestearyl dimethicones, especially those sold by the company Dow Corningunder the trade names DC2503 and DC25514, and mixtures thereof.

The pasty fatty substance(s) may be present in a proportion of from 0 to60% by weight relative to the total weight of the composition,preferably in a proportion of 0.1-45% by weight and even more preferablyin a proportion of 2-30% by weight.

According to the invention, the composition may furthermore containcolouring matter which may be a pigment or a pearlescent agent asdefined above, or a soluble compound chosen from lipophilic dyes,hydrophilic dyes, and mixtures thereof.

The liposoluble dyes are, for example, Sudan red, DC Red 17, DC Green 6,β-carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DCOrange 5, quinoline yellow and annatto. The hydrophilic dyes are forexample beet juice and methylene blue. Each type of dye can representfrom 0% to 20% of the weight of the composition and better still from0.1% to 6% (if present).

The composition according to the invention may be manufactured by knownmethods, generally used in the cosmetic or dermatological field. It maybe manufactured by the method which consists in heating the polymer atleast to its softening point, adding thereto the pasty compounds and/orthe optional waxes, the oil(s), the organogelling agent, if necessarythe amphiphilic compound(s), the colouring matter and/or the solidparticles, and the additives, and then in mixing the whole until atransparent, clear solution is obtained. The homogeneous mixtureobtained can then be cast in a suitable mould such as a lipstick mould,or directly into the packaging articles (especially a case or dish).

The subject of the invention is also a make-up structured solidcomposition for the skin, the lips and/or the superficial body growths,containing at least one pigment in a sufficient quantity for applyingmake-up to the skin, the lips and/or the superficial body growths and aliquid continuous fatty phase comprising at least one silicone oilstructured with at least one polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,        the liquid fatty phase consisting partially or totally of        silicone oil(s) and containing a non-polymeric organogelling        agent,

the said composition being provided in the form of a solid, and thepigment, the liquid fatty phase, the organogelling agent and the polymerforming a physiologically acceptable medium.

This make-up composition is preferably self-supporting.

The subject of the invention is also a lipstick structured composition,containing at least one pigment in a sufficient quantity for applyingmake-up to the lips and a liquid continuous fatty phase comprising atleast one silicone oil structured with at least one polymer (homopolymeror copolymer) having a weight-average molecular mass ranging from 500 to500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,        the liquid fatty phase consisting partially or totally of        silicone oil(s) and of an organogelling agent,

the said composition being provided in the form of a solid, and thepigment, the liquid fatty phase and the polymer forming aphysiologically acceptable medium.

The composition of the invention may be provided in the form of a cakemascara, an eyeliner, a foundation, a lipstick, a blusher, amake-up-removing product, a make-up product for the body, an eyeliner ora face powder, or a concealer product.

The subject of the invention is also a make-up stick for the skin, thelips and/or the superficial body growths, and in particular for thelips, containing at least one pigment in a sufficient quantity forapplying make-up to the skin, the lips and/or the superficial bodygrowths and a liquid continuous fatty phase comprising at least onesilicone oil structured with at least one polymer (homopolymer orcopolymer) having a weight-average molecular mass ranging from 500 to500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase consisting partially or totally of siliconeoil(s) and of organogelling agent, the pigment, the fatty phase and thepolymer forming a physiologically acceptable medium.

The invention relates to a cosmetic care, make-up or treatment methodfor the keratinous materials of human beings, comprising the applicationto the keratinous materials of a cosmetic composition in accordance withthe invention.

The subject of the invention is also the use of a sufficient quantity ofat least one polymer (homopolymer or copolymer) having a weight-averagemolecular mass ranging from 500 to 500 000, containing at least onemoiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,        in a cosmetic composition or for the manufacture of a        physiologically acceptable composition, containing a liquid        continuous fatty phase comprising at least one silicone oil, the        liquid fatty phase consisting partially or totally of silicone        oil(s) having a flash point equal to or greater than 40° C. and        greater than the softening point of the polymer and containing        an organogelling agent, to structure the said composition in the        form of a self-supporting solid with a hardness ranging from 20        to 2 000 gf and preferably from 20 to 900 gf and even better        from 20 to 600 gf.

The subject of invention is also the use of a continuous liquid fattyphase comprising at least one silicone oil, essentially structured witha sufficient quantity of at least one polymer (homopolymer or copolymer)having a weight-average molecular mass ranging from 500 to 500 000,containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase consisting partially or totally of volatileoil(s) having a flash point equal to or greater than 40° C. and greaterthan the softening point of the polymer and containing an organogellingagent, in a cosmetic composition or for the manufacture of aphysiologically acceptable, rigid, self-supporting, glossy and/ornon-migrating composition, on the condition that the compositioncomprises at least 10% by mass of a non-volatile oil and/or of a pastyor viscous product.

The subject of the invention is also the use of a sufficient quantity ofat least one polymer (homopolymer or copolymer) having a weight-averagemolecular mass ranging from 500 to 500 000, containing at least onemoiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

in a cosmetic composition or for the manufacture of a physiologicallyacceptable composition, containing a liquid continuous fatty phasecomprising at least one silicone oil and at least one organogellingagent, to structure the said composition in the form of aself-supporting solid.

The subject of the invention is also the use of a continuous liquidfatty phase comprising at least one silicone oil, essentially structuredwith a sufficient quantity of at least one polymer (homopolymer orcopolymer) having a weight-average molecular mass ranging from 500 to500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in a chain of the moiety or in the form of        a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase consisting partially or totally of volatileoil(s) having a flash point equal to or greater than 40° C. and greaterthan the softening point of the gelling polymer and containing anorganogelling agent, in a cosmetic composition or for the manufacture ofa physiologically acceptable composition, as agent for limiting themigration of the said composition, on the condition that the compositioncomprises at least 10% by mass of a non-volatile oil and/or of a pastyor viscous product.

According to an advantageous characteristic of these uses, thecomposition has a hardness of 20 to 2 000 gf, preferably of 20 to 900 gfand even better of 20 to 600 gf.

The invention finally relates to a cosmetic method for limiting themigration of a cosmetic composition containing a liquid fatty phasecomprising at least one silicone oil, consisting in structuring the saidfatty phase with a sufficient quantity of at least one polymer(homopolymer or copolymer) having a weight-average molecular massranging from 500 to 500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof, provided that at        least one group is different from an ester group,        the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase consisting partially or totally of siliconeoil(s) and containing at least one organogelling agent.

DETAILED DISCLOSURE OF THE INVENTION

The invention is illustrated in greater detail in the following examplesof make-up formulation. The quantities are given as % by mass. Thechemical compounds are given mainly as the CTFA (“International CosmeticIngredient Dictionary”) name. The viscosities are measured at 25° C. andat atmospheric pressure.

Example 1 Lipstick

Composition Cyclopentasiloxane D5 qs 100% Phenyltrimethicone (DC 556from Dow Corning, of 20 cSt)  5% Hydrogenated isoparaffin (Parleam ®from Nippon Oil Fats)  5% Hydrophobic treated pigments (red and yellowiron oxides and 10% titanium oxide) Silicone polyamide of Example 1 ofU.S. Pat. No. 5,981,680 15% Preservative qs Organogelling agent(dibutylamide of N-laurylglutamic acid)  5% Perfume qs

The pigments have the following colour indices (CI):

red iron oxide CI: 77491

yellow iron oxide CI: 77492

titanium oxide CI: 77891

This lipstick is obtained by heating the organogelling agent and thepolymer until the whole melts, followed by addition of the Parleam andof a portion of the phenyltrimethicone. In parallel, the pigments andthe other portion of the phenyltrimethicone are mixed at roomtemperature and then they are ground in a three-roll mill. This groundmaterial is added to the molten mixture of wax and of silicone oils, andthen the whole is homogenized. The whole is cooled by at least 20° C.relative to the melting point of the mixture and the cyclopentasiloxaneD5 is then added, followed by the preservative and the perfume, stillwith stirring. The mixture is then cast in a suitable mould.

The product thus obtained has properties of staying power, in particularof the colour, of slipperiness and of non-greasiness.

Example 2 Foundation

Composition Cyclopentasiloxane D5 qs 100% PDMS α-ωoxyethylenated/oxypropylenated in  3% cyclopentasiloxane D5 (Abil EM 90from Goldschmmitd) Phenyltrimethicone (DC 556 from Dow Corning, of 20cSt)  5% Hydrogenated isoparaffin (Parleam ® from Nippon Oil Fats)  5%Hydrophobic treated pigments (red and yellow iron oxides and 10%titanium oxide) Silicone polyamide of Example 2 of U.S. Pat. No.5,981,680 15% Preservative qs Organogelling agent¹  2% Perfume qs1) The organogelling agent is a cis-trans mixture of the compound offormula:

The pigments have the following colour indices (CI):

red iron oxide CI: 77491

yellow iron oxide CI: 77492

brown iron oxide CI: 77491

titanium oxide CI: 77891

This foundation is obtained by heating the organogelling agent and thepolymer in the mixture of oils until the whole melts, followed byaddition of the Parleam and of a portion of the phenyltrimethicone. Inparallel, the pigments, Abil EM 90 and the other portion of thephenyltrimethicone are mixed at room temperature and then they areground in a three-roll mill. This ground material is added to the moltenmixture of wax and of silicone oils, and then the whole is homogenizedby means of magnetic stirring. The whole is cooled by at least 20° C.relative to the melting point of the mixture and the cyclopentasiloxaneD5 is then added, followed by the preservative and the perfume, stillwith stirring. The mixture is then cast in a suitable mould.

The product thus obtained has properties of staying power, in particularof the colour, of slipperiness and of non-greasiness.

Example 3 Anhydrous Foundation

Composition PDMS (5 cSt) qs 100% Phenyltrimethicone (DC 556)  5% PDMS(300 cSt)  5% Hydrophobic treated pigments (red and yellow iron oxidesand 10% titanium oxide, treated with perfluoroalkyl phosphate) Siliconepolyamide of Example 2 of U.S. Pat. No. 5,981,680 12% Hydrophobictreated silica (trimethylsiloxyl treatment)  3% Preservative qsOrganogelling agent¹  4% Perfume qs ¹The organogelling agent is acis-trans mixture of the compound of formula:

This foundation is prepared like the lipstick of Example 1, the silicabeing introduced at the same time as the phenyltrimethicone into thepigmented ground material and the isononyl isononanoate being introducedinto the mixture of wax and of silicone oils.

It has properties of non-greasiness, slipperiness, mattness and goodstaying power over time, in particular of the colour.

The particles used are hydrophobic (or even better lipophilic)particles.

REFERENCES

-   [1] EP-A-1 068 856-   [2] WO-A-01/97758-   [3] U.S. Pat. No. 5,874,069-   [4] U.S. Pat. No. 5,919,441-   [5] U.S. Pat. No. 6,051,216-   [6] WO-A-02/17870-   [7] WO-A-02/17871-   [8] EP-A-1 177 784-   [9] U.S. Pat. No. 5,412,004-   [10] EP-A-1 048 686-   [11] U.S. Pat. No. 5,981,680-   [12] Article by D. Robb, 1997, pp. 209-263, chapter 8 and by P.    Terech “Specialist Surfactants”-   [13] FR-A-2 796 276-   [14] FR-A-2 811 552-   [15] WO-93/23008-   [16] WO-A-01/07007-   [17] Article by R. J. H. Hafkamp, Chem. Commun., 1997, pages 545-546-   [18] Article J. Org. Chem., vol. 64, No. 2, 412-26 (1999)-   [19] Article by M. Jokic, J. Chem. Soc., Chem. Commun., pages    1723-24 (1995)-   [20] Article by K. Hanabusa, Chemistry Letters, pp. 1070-71, 2000-   [21] Article by K. Hanabusa, Chemistry Letters, pp. 767-8, 1999-   [22] Article by X. Luo, Chem. Commun., pp. 2091-92, 2000-   [23] Article by T. Shimizu, J. Am. Chem. Soc., 119, pp. 2812-18,    1997-   [24] Article by K. Hanabusa, Adv. Mater., 9, No. 14, 1997, pp.    1095-1097-   [25] Article by K. Hanabusa, Colloïd Polym. Sci., 276, pp. 252-59,    1998-   [26] WO-A-00/61080-   [27] WO-A-00/61081-   [28] U.S. Pat. No. 6,156,325-   [29] Article by K. Hanabusa, Agnew. Chem., 108, 1997, 17, pp.    2086-2088-   [30] U.S. Pat. No. 5,480,637-   [31] EP-A-616 842-   [32] EP-A-665 007-   [33] U.S. Pat. No. 5,776,494-   [34] U.S. Pat. No. 5,429,816-   [35] Article by K. Hanabusa, J. Chem. Soc., Chem. Commun., 1993, pp.    390-92-   [36] EP-A-1 064 925-   [37] Article by P. Terech, Chem. Rev., 97, 3133-59, 1997-   [38] Article by K. Hanabusa, J. Colloïd and Int. Sci., 224, pp.    231-44, 2000-   [39] U.S. Pat. No. 6,002,048-   [40] WO-A-99/06473-   [41] U.S. Pat. No. 6,353,076

1. Care and/or make-up cosmetic composition comprising a liquid fattyphase comprising at least one volatile silicone oil and at least onevolatile non-silicone oil, structured with a gelling systemcomprising: 1) at least one nylon 611/dimethicone copolymer, 2) at leastone non-polymeric organogelling agent, wherein the organogelling agentis selected from the group consisting of: (1)—N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane, (2)—N,N′-bis(dodecanoyl)-1,3-diaminocyclohexane, (3)—N,N′-bis(dodecanoyl)-1,4-diaminocyclohexane, (4)—N,N′-bis(dodecanoyl)-1,2-ethylenediamine, (5)—N,N′-bis(dodecanoyl)-1-methyl-1,2-ethylenediamine, (6)—N,N′-bis(dodecanoyl)-1,3-diaminopropane, (7)—N,N′-bis(dodecanoyl)-1,12-diaminododecane, (8)—N,N′-bis(dodecanoyl)-3,4-diaminotoluene, (9) —at least one compoundchosen from the compounds of formula (XV):

in which the groups R⁴⁸, which are identical or different, are chosenfrom a hydrogen atom and saturated, linear and branched hydrocarbonchains, the said hydrocarbon chains containing from 1 to 6 carbon atoms;the groups Z, which are identical or different, each represent a groupchosen from the following groups: —CO—S—R⁴⁹; —CO—NHR⁴⁹; —NH—COR⁴⁹ and—S—COR⁴⁹; in which the groups R⁴⁹, which may be identical or different,are chosen from: a hydrogen atom, aryl groups, aralkyl groups, andsaturated hydrocarbon chains chosen from linear, branched and cyclichydrocarbon chains, containing from 1 to carbon atoms, optionallysubstituted with at least one group chosen from aryl, ester, amide andurethane groups; and/or optionally comprising at least one heteroatomchosen from O, S and N; and/or optionally substituted with at least onefluorine atom and/or one hydroxyl radical, (10) —sterol derivativesselected from the group consisting of lanosterol, dihydrolanosterol, andcholesterol esters, (11) —diamides of formula (XXV) or (XXVI):R⁴⁴—X—CO—NH—R⁴⁵—NH—CO—X—R⁴⁴  (XXV)orR⁴⁴—CO—NH—R⁴⁵—NH—CO—R⁴⁴  (XXVI) in which the groups R⁴⁴, which may beidentical or different, represent a saturated, linear or branched C₈-C₆₀hydrocarbon chain, the group(s) R⁴⁴ optionally comprising a hydroxylgroup or at least one heteroatom such as N, O, S or Si, R⁴⁵ is ahydrocarbon-based group chosen from linear, branched and cyclic C₁ toC₅₀ groups and C₅ to C₈ arylene groups optionally substituted with oneor more C₁-C₄ alkyl groups, and X represents —O— or —NH—, and mixturesthereof, and (12) —trans-(1R,2R)-bis(undecylcarbonylamino)cyclohexane offormula:

the liquid fatty phase and the gelling system forming a physiologicallyacceptable medium, and 3) at least one pigment in an amount sufficientto provide a coloring effect to keratin materials upon application. 2.Composition according to claim 1, in which the volatile silicone oil hasa flash point equal to or greater than 40° C. and greater than thesoftening point of the gelling system.
 3. Composition according to claim1, in which the volatile silicone oil is chosen from the groupconsisting of the following compounds: octyltrimethicone,hexyltrimethicone, octamethylcyclotetrasiloxane D4,dodecamethylcyclohexasiloxane D6, heptamethyloctyltrisiloxane,decamethyltetrasiloxane, dodecamethylpentasiloxane, polydimethylsiloxaneof 1.5 cSt, polydimethylsiloxane of 2 cSt, polydimethylsiloxane of 3cSt, polydimethylsiloxane of 5 cSt, and mixtures thereof.
 4. Compositionaccording to claim 1, in which the volatile silicone oil has a flashpoint of 40 to 135° C.
 5. Composition according to claim 1, in which theliquid fatty phase contains at least 30% silicone oil with respect tothe total weight of the composition.
 6. Composition according to claim1, in which the volatile silicone oil represents from 3 to 89.4% of thetotal weight of the composition.
 7. Composition according to claim 1,further comprising at least one filler comprising solid particles. 8.Composition according to claim 7, in which the solid particles arehydrophobic particles.
 9. Composition according to claim 8, in which thesolid particles are hydrophilic particles, coated with a film ofhydrophobic compound.
 10. Composition according to claim 7, in which thesolid particles are hydrophilic particles and the composition furthercomprises an amphiphilic silicone.
 11. Composition according to claim 1,in which the at least one pigment is chosen from zinc oxides, ironoxides, titanium oxides and mixtures thereof.
 12. Composition accordingto claim 1, in which the at least one nylon 611/dimethicone copolymerrepresents from 0.5 to 80% of the total weight of the composition. 13.Composition according to claim 1, in which the liquid fatty phasefurther contains a non-volatile non-silicone oil.
 14. Compositionaccording to claim 1, in which the liquid fatty phase represents from 5to 99% of the total weight of the composition.
 15. Composition accordingto claim 1, in which in the at least one volatile non-silicone oil is atleast one selected from the group consisting of isododecane,isohexadecane, isohexyl neopentanoate, and isodecyl neopentanoate. 16.Composition according to claim 1, in which in the at least one volatilenon-silicone oil is at least one selected from the group consisting ofisododecane and isohexadecane.
 17. Composition according to claim 16, inwhich the at least one volatile non-silicone oil is isododecane. 18.Composition according to claim 1, in which the organogelling agentcomprises at least one compound chosen from:N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,3-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,4-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,2-ethylenediamine,N,N′-bis(dodecanoyl)-1-methyl-1,2-ethylenediamine,N,N′-bis(dodecanoyl)-1,3-diaminopropane,N,N′-bis(dodecanoyl)-1,12-diaminododecane, andN,N′-bis(dodecanoyl)-3,4-diaminotoluene.
 19. Composition according toclaim 1, in which the organogelling agent comprises at least onecompound chosen from the compounds of formula (XV):

in which the groups R⁴⁸, which are identical or different, are chosenfrom a hydrogen atom and saturated, linear and branched hydrocarbonchains, the said hydrocarbon chains containing from 1 to 6 carbon atoms;the groups Z, which are identical or different, each represent a groupchosen from the following groups: —CO—S—R⁴⁹; —CO—NHR⁴⁹; —NH—COR⁴⁹ and—S—COR⁴⁹; in which the groups R⁴⁹, which may be identical or different,are chosen from: a hydrogen atom, aryl groups, aralkyl groups, andsaturated hydrocarbon chains chosen from linear, branched and cyclichydrocarbon chains, containing from 1 to carbon atoms, optionallysubstituted with at least one group chosen from aryl, ester, amide andurethane groups; and/or optionally comprising at least one heteroatomchosen from O, S and N; and/or optionally substituted with at least onefluorine atom and/or one hydroxyl radical.
 20. Composition according toclaim 19, in which in the formula (XV), each R⁴⁸ is a hydrogen atom. 21.Composition according to claim 19, in which in the formula (XV), each Zis chosen from the groups CONHR⁴⁹ and NH—COR⁴⁹.
 22. Compositionaccording to claim 19, in which in the formula (XV), R⁴⁹ is chosen fromaryl groups; aralkyl groups in which the alkyl portion is a linear orbranched alkyl chain comprising 12 to 16 carbon atoms; and linear andbranched C₁₁-C₁₈ alkyl chains.
 23. Composition according to claim 19, inwhich the organogelling agent is chosen from:cis-1,3,5-tris(dodecylaminocarbonyl)cyclohexane,cis-1,3,5-tris(octadecylaminocarbonyl)cyclohexane,cis-1,3,5-tris[N-(3,7-dimethyloctyl)aminocarbonyl]-cyclohexane,trans-1,3,5-trimethyl-1,3,5-tris(dodecylaminocarbonyl)cyclohexane, andtrans-1,3,5-trimethyl-1,3,5-tris(octadecylaminocarbonyl)-cyclohexane.24. Composition according to claim 1, in which the organogelling agentis present in a quantity ranging from 0.1% to 80% by weight relative tothe total weight of the composition.
 25. Composition according to claim1, in which the organogelling agent is present in a quantity rangingfrom 0.5% to 60% by weight relative to the total weight of thecomposition.
 26. Composition according to claim 1, in which thepolymer/non-polymeric organogelling agent mass ratio is in the rangefrom 20 to 0.15.
 27. Composition according to claim 1, wherein thecomposition further comprises at least one cosmetic or dermatologicalactive agent.
 28. Composition according to claim 1, wherein the activeagent is chosen from essential oils, vitamins, moisturizers, sunscreens,cicatrizing agents and ceramides.
 29. Composition according to claim 1,wherein comprises at least one additive chosen from dyes that aresoluble in polyols or in the fatty phase, antioxidants, essential oils,preserving agents, perfumes, liposoluble polymers, liquid-fatty-phasegelling agents, waxes, gums, resins, surfactants, water, emollients,moisturizers, vitamins, liquid lanolin, essential fatty acids,lipophilic sunscreens or sunscreens that are soluble in polyols, lipidvesicles, and mixtures thereof.
 30. Composition according to claim 1,wherein the composition further comprises an amphiphilic compound whichis liquid at room temperature, having a hydrophilic/lipophilic balancevalue of less than
 12. 31. Composition according to claim 1, wherein thecomposition comprises at least one colouring matter other than apigment.
 32. Composition according to claim 1, in the form of ananhydrous stick.
 33. Composition according to claim 1, in the form of amake-up.
 34. Composition according to claim 33, wherein the compositionis self-supporting.
 35. Composition according to claim 1, in the form ofa lipstick.
 36. Composition according to claim 1, in the form of a cakemascara, an eyeliner, a foundation, a lipstick, a blusher, amake-up-removing or deodorant product, a make-up product for the body,an eyeshadow or a face powder, or a concealer product.
 37. A method ofmaking up a keratinous material comprising applying the composition ofclaim 1 to the keratinous material.
 38. Composition according to claim1, in which the organogelling agent comprises at least one sterolderivative selected from the group consisting of lanosterol,dihydrolanosterol, and cholesterol esters.
 39. Composition according toclaim 1, in which the organogelling agent comprises at leasttrans-(1R,2R)-bis(undecylcarbonylamino)cyclohexane of formula:


40. Composition according to claim 1, in which the organogelling agentcomprises at least one compound chosen from diamides of formula (XXV) or(XXVI):R⁴⁴—X—CO—NH—R⁴⁵—NH—CO—X—R⁴⁴  (XXV)orR⁴⁴—CO—NH—R⁴⁵—NH—CO—R⁴⁴  (XXVI) in which the groups R⁴⁴, which may beidentical or different, represent a saturated, linear or branched C₈-C₆₀hydrocarbon chain, the group(s) R⁴⁴ optionally comprising a hydroxylgroup or at least one heteroatom such as N, O, S or Si, R⁴⁵ is ahydrocarbon-based group chosen from linear, branched and cyclic C₁ toC₅₀ groups and C₅ to C₈ arylene groups optionally substituted with oneor more C₁-C₄ alkyl groups, and X represents —O— or —NH—, and mixturesthereof.
 41. A method of making a composition comprising combining atleast one nylon 611/dimethicone copolymer with a liquid continuous fattyphase comprising at least one volatile silicone oil and at leastone-volatile non-silicone oil, the liquid fatty phase comprisingsilicone oil(s) having a flash point equal to or greater than 40° C. andgreater than the softening point of the and an organogelling agent,wherein the organogelling agent is selected from the group consistingof: (1) —N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane, (2)—N,N′-bis(dodecanoyl)-1,3-diaminocyclohexane, (3)—N,N′-bis(dodecanoyl)-1,4-diaminocyclohexane, (4)—N,N′-bis(dodecanoyl)-1,2-ethylenediamine, (5)—N,N′-bis(dodecanoyl)-1-methyl-1,2-ethylenediamine, (6)—N,N′-bis(dodecanoyl)-1,3-diaminopropane, (7)—N,N′-bis(dodecanoyl)-1,12-diaminododecane, (8)—N,N′-bis(dodecanoyl)-3,4-diaminotoluene, (9) —at least one compoundchosen from the compounds of formula (XV):

in which the groups R⁴⁸, which are identical or different, are chosenfrom a hydrogen atom and saturated, linear and branched hydrocarbonchains, the said hydrocarbon chains containing from 1 to 6 carbon atoms;the groups Z, which are identical or different, each represent a groupchosen from the following groups: —CO—S—R⁴⁹; —CO—NHR⁴⁹; —NH—COR⁴⁹ and—S—COR⁴⁹; in which the groups R⁴⁹, which may be identical or different,are chosen from: a hydrogen atom, aryl groups, aralkyl groups, andsaturated hydrocarbon chains chosen from linear, branched and cyclichydrocarbon chains, containing from 1 to carbon atoms, optionallysubstituted with at least one group chosen from aryl, ester, amide andurethane groups; and/or optionally comprising at least one heteroatomchosen from O, S and N; and/or optionally substituted with at least onefluorine atom and/or one hydroxyl radical, (10) —sterol derivativesselected from the group consisting of lanosterol, dihydrolanosterol, andcholesterol esters, (11) —diamides of formula (XXV) or (XXVI):R⁴⁴—X—CO—NH—R⁴⁵—NH—CO—X—R⁴⁴  (XXV)orR⁴⁴—CO—NH—R⁴⁵—NH—CO—R⁴⁴  (XXVI) in which the groups R⁴⁴, which may beidentical or different, represent a saturated, linear or branched C₈-C₆₀hydrocarbon chain, the group(s) R⁴⁴ optionally comprising a hydroxylgroup or at least one heteroatom such as N, O, S or Si, R⁴⁵ is ahydrocarbon-based group chosen from linear, branched and cyclic C₁ toC₅₀ groups and C₅ to C₈ arylene groups optionally substituted with oneor more C₁-C₄ alkyl grow s, and X represents —O— or —NH—, and mixturesthereof, (12) —trans-(1R,2R)-bis(undecylcarbonylamino)cyclohexane offormula:

and at least one pigment in an amount sufficient to provide a coloringeffect to keratin materials upon application, to form a compositionwhich is in the form of a self-supporting solid with a hardness rangingfrom 20 to 2 000 gf.
 42. Care and/or make-up cosmetic compositioncomprising a liquid fatty phase comprising at least one volatilesilicone oil and at least one volatile non-silicone oil, structured witha gelling system comprising: 1) at least one nylon 611/dimethiconecopolymer, 2) at least one non-polymeric organogelling agent, whereinthe organogelling agent is selected from the group consisting of:N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,3-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,4-diaminocyclohexane,N,N′-bis(dodecanoyl)-1,2-ethylenediamine,N,N′-bis(dodecanoyl)-1-methyl-1,2-ethylenediamine,N,N′-bis(dodecanoyl)-1,3-diaminopropane,N,N′-bis(dodecanoyl)-1,12-diaminododecane,N,N′-bis(dodecanoyl)-3,4-diaminotoluene, at least one compound chosenfrom the compounds of formula (XV):

in which the groups R⁴⁸, which are identical or different, are chosenfrom a hydrogen atom and saturated, linear and branched hydrocarbonchains, the said hydrocarbon chains containing from 1 to 6 carbon atoms; the groups Z, which are identical or different, each represent a groupchosen from the following groups: —CO—S—R⁴⁹; —CO—NHR⁴⁹; —NH—COR⁴⁹ and—S—COR⁴⁹; in which the groups R⁴⁹, which may be identical or different,are chosen from:  a hydrogen atom,  aryl groups,  aralkyl groups, and saturated hydrocarbon chains chosen from linear, branched and cyclichydrocarbon chains, containing from 1 to carbon atoms, optionallysubstituted with at least one group chosen from aryl, ester, amide andurethane groups; and/or optionally comprising at least one heteroatomchosen from O, S and N; and/or optionally substituted with at least onefluorine atom and/or one hydroxyl radical, sterol derivatives selectedfrom the group consisting of lanosterol, dihydrolanosterol, andcholesterol esters, andtrans-(1R,2R)-bis(undecylcarbonylamino)cyclohexane of formula:

the liquid fatty phase and the gelling system forming a physiologicallyacceptable medium, and 3) at least one pigment in an amount sufficientto provide a coloring effect to keratin materials upon application.